Accepted Manuscript

Bidentate and tridentate coordination modes of bis(3-methylindolyl)-2-pyridylmethane

in complexes of aluminum and gallium: Structural characterization of bridging N-
indolide in a dialuminum complex

Bassam N. Fneich, Anirban Das, Kristin Kirschbaum, Mark R. Mason

PII: S0022-328X(18)30502-3
DOI: 10.1016/j.jorganchem.2018.07.024
Reference: JOM 20511

To appear in: Journal of Organometallic Chemistry

Received Date: 20 June 2018

Revised Date: 17 July 2018
Accepted Date: 18 July 2018

Please cite this article as: B.N. Fneich, A. Das, K. Kirschbaum, M.R. Mason, Bidentate and tridentate
coordination modes of bis(3-methylindolyl)-2-pyridylmethane in complexes of aluminum and gallium:
Structural characterization of bridging N-indolide in a dialuminum complex, Journal of Organometallic
Chemistry (2018), doi: 10.1016/j.jorganchem.2018.07.024.

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 ACCEPTED MANUSCRIPT

Bidentate and Tridentate Coordination Modes of Bis(3-methylindolyl)-2-

pyridylmethane in Complexes of Aluminum and Gallium: Structural

Characterization of Bridging N-Indolide in a Dialuminum Complex

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Bassam N. Fneich, Anirban Das, Kristin Kirschbaum, and Mark R. Mason*

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Department of Chemistry and Biochemistry, School of Green Chemistry and Engineering,

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MS 602, University of Toledo, Toledo, Ohio 43606-3390
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*Author to whom correspondence should be addressed
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E-mail: mmason5@utoledo.edu
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Graphic for Table of Contents and Abstract

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+ Et3Al NH + 2 Me3Al

N NH

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U SC
AN
M
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Abstract

Reactions of a slight excess of trialkylaluminum or tri-tert-butylgallium with bis(3-

methylindolyl)-2-pyridylmethane (1) produced monomeric, tripodal complexes (2-C5H4N)HC(3-

CH3C8H4N)2MR (M = Al, R = Me (2a), Et (2b), iBu (2c), tBu (2d); M = Ga, R = tBu (3)). Under

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more mild reaction conditions and with a stoichiometric amount of tri-tert-butylaluminum or tri-

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tert-butylgallium, complexes (2-C5H4N)HC(3-CH3C8H4N)(3-CH3C8H4NH)MtBu2 (M = Al (4),

Ga (5)) were isolated. Whereas di-deprotonated 1 adopts a tridentate coordination mode in 2a-2d

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and 3, mono-deprotonated 1 adopts a bidentate coordination mode in 4 and 5. Reaction of 1 with

two equivalents of trimethylaluminum or triethylaluminum yields dialuminum complexes (2-

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C5H4N)HC(3-CH3C8H4N)2Al2R4 (R = Me (6a), Et (6b). In addition to NMR (1H, 13C)
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spectroscopy, compounds 1, 2b•0.25C6H6, 4, and 6a•C7H8 were further characterized by X-ray

crystallography. The solid-state structure for 6a•C7H8 confirms the presence of a bridging µ2-
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η1:η1-N-indolide moiety. Variable-temperature NMR spectra of toluene solutions of 6a and 6b

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are consistent with retention of a bridging µ2-η1:η1-N-indolide group at low temperature, which
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becomes fluxional in solution at higher temperatures. A mechanism for the fluxional process is

proposed.
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Keywords: Aluminum; Indolide complexes; Nitrogen-donor ligands

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1. Introduction

Lewis acids of aluminum are of continuing importance for activation of small molecules,

as catalysts for a variety of organic transformations [1,2], and as catalysts and co-catalysts for the

oligomerization and polymerization of epoxides [3], lactides [4], lactones [4,5], and alkenes

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[1,2,6,7]. For example, Lewis acids of aluminum are highly active co-catalysts for cationic,

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group 4 metallocene-catalyzed alkene polymerizations in which aluminates function as weakly

coordinating anions and/or hydrolyzed aluminum alkyls and various alanes act as methide

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abstractors [7]. Furthermore, the groups of Jordan [8], Gibson [9], and Sen [10] have

demonstrated that transition-metal-free aluminum catalysts can polymerize ethylene. Jordan and

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Gibson demonstrated the effectiveness of cationic amidinate and Schiff base complexes,
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respectively, whereas Sen successfully employed combinations of Al(C6F5)3, B(C6F5)3, or

[Me2HNC6H5][B(C6F5)4] and an aluminum alkyl for the copolymerization of ethylene and

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propylene. There is continued interest in new group 13 Lewis acids for these and related
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applications, partially promoted by heavy interest in the Frustrated Lewis Pair approach for
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activation of small molecules [11].

We have focused on the use of N-pyrrolide and N-indolide ligands to increase Lewis
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acidity and/or decrease basicity of main group [12] and transition metal compounds [13].

Advantages of N-pyrrolide, N-indolide, and N-carbazolide moieties for stabilizing electrophilic

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metal centers include their electron-withdrawing ability, reduced N→M π-donating ability, and
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reduced tendency for M−N−M bridging relative to that for common amido ligands [12-14]. With

respect to our interests in complexes of aluminum, we were further intrigued by reports that

pyrrolide, indolide, and carbazolide complexes of aluminum function as catalysts, co-catalysts, or

catalyst precursors for aluminum-catalyzed oligomerization of ethylene [15], transition metal-

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catalyzed polymerization of ethylene [16], and chromium-catalyzed trimerization of ethylene to 1-

hexene in the Chevron-Phillips process [17] and in similar chemistry patented by Sumitomo

Chemical [18] and Sasol Technology [19].

In this contribution, we focus on the use of deprotonated 2,2’-bis(3-methylindolyl)-2-

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pyridylmethane (1) as a bidentate ligand and as a tridentate ligand capable of adopting tripodal

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coordination upon binding of the pyridyl nitrogen to an electrophilic metal. These possible

coordination modes resemble those for "heteroscorpionate" bis(pyrazolyl)borate ligands [20]. We

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hypothesized that tridentate coordination of deprotonated 1 to aluminum, followed by alkide

abstraction from aluminum under appropriate conditions, may result in formation of cationic

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tripodal complexes with high Lewis acidity. Tripodal, non-atrane complexes of aluminum and
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boron ligated by tridentate amido ligands are relatively rare. Zhu and Chen published the first

neutral tripodal complexes of aluminum and boron ligated by tridentate amido ligands, and
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crystallographically characterized the complexes HC(SiMe2NAr)3B (Ar = p-tolyl) and

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HC(SiMe2NR)3Al(THF) (R = CH2Ph, p-tolyl) [21]. We previously investigated the synthesis of

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similar complexes of aluminum using a tris(3-methylindolyl)methane scaffold, but those

complexes crystallized poorly and were not amenable to crystallographic characterization [22].
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Herein we report the synthesis and characterization of 2,2’-bis(3-methylindolyl)-2-

pyridylmethane (1), the preparation of neutral tripodal aluminum alkyl complexes 2a-2d and
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gallium analogue 3, as well as examples of deprotonated 1 serving as a bidentate ligand in

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complexes 4 and 5. We report the isolation and characterization of bimetallic complexes 6a and

6b, including the crystallographic confirmation of a bridging µ2-η1:η1-N-indolide moiety in

6a•C7H8. We also comment on unsuccessful preliminary attempts to abstract hydride or alkide

from 2a-2d to generate cationic, tripodal Lewis acids.

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R
N M
N N
N

NH HN H

1 2a M = Al, R = Me

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2b M = Al, R = Et
2c M = Al, R = iBu
2d M = Al, R = tBu
R = tBu

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3 M = Ga,

R R
N R

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t R Al Al
N Bu
M N N
t
N N Bu
H

4 M = Al
U 6a R = Me
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5 M = Ga 6b R = Et
M

2. Results and discussion

2.1. Ligand synthesis. Bis(indolyl)methanes are commonly prepared from acid-catalyzed

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reactions of an indole derivative with an aldehyde [23]. Since indoles preferentially react with
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electrophiles at C3, the use of 3-methylindole directs reactions to C2 (Scheme 1), resulting in

2,2’-bis(indolyl)methanes suitable for use as dianionic, bidentate ligands to main group and
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transition metals upon deprotonation [23,24].

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In this work, bis(3-methylindolyl)-2-pyridylmethane (1) was prepared by an acid-

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catalyzed condensation strategy as shown in Scheme 1. Condensation of one equivalent of 2-

pyridinecarboxaldehyde with two equivalents of 3-methylindole in ethanol, catalyzed by a few

drops of sulfuric acid, produced a bright yellow precipitate [1•H][HSO4], which was isolated by

filtration in 49% yield. Deprotonation of [1•H][HSO4] was accomplished by stirring a

stoichiometric amount of Amberlite IRA-67 in a suspension of [1•H][HSO4] in acetonitrile.

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5
4 6
O H 3a
3 7
7a
10 11 2
N ethanol, H+ NH NH
Amberlite IRA-67
2 + 9
reflux, 20h
NH CH3CN, 20 oC NH
N NH N
H 8
HSO4-

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[1H][HSO4] 1

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Scheme 1. Synthesis of bis(3-methylindolyl)-2-pyridylmethane (1). Numbering scheme for

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compound 1 shown to aid discussion of NMR data and assignments.

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Although the protonated ligand is essentially insoluble in acetonitrile and other common solvents,
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except for DMSO, neutral 1 afforded after deprotonation of the pyridine residue is very soluble in
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acetonitrile and other polar solvents. After a clear solution was obtained, Amberlite IRA-67 beads

were removed by filtration and solvent was removed in vacuo to afford 1 in overall 46% yield.
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Deprotonation using other bases, such as sodium hydroxide and triethylamine, were successful,
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but less convenient and resulted in lower yields than those obtained using Amberlite. Amberlite

gave nearly quantitative yield.

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The constitution of 1 was confirmed by HRMS and elemental analysis, and the proposed
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structure is supported by NMR spectroscopy. The 1H NMR spectrum of 1 in CDCl3 exhibits a

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broad singlet at 9.05 ppm corresponding to two NH protons, a singlet methine resonance at 5.93

ppm, and a singlet at 2.32 ppm assigned to indole methyl protons. The downfield indolyl NH

resonance at 9.05 ppm suggests the presence of hydrogen bonding with the pyridyl nitrogen.

Resonances for the indole moieties are typical and appear as doublets at 7.49 and 7.29 ppm for

H7 and H4 and triplets at 7.11 and 7.06 ppm assigned to H5 and H6, respectively. Integration
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confirms a 1 to 2 ratio of pyridyl to indolyl groups. Also, the absence of the broad resonance at

5.2 ppm for the protonated pyridine nitrogen atom in [1•H][HSO4] indicates that deprotonation

was successful. Moreover, these resonances, along with 13C NMR resonances, fall in the range of

the corresponding chemical shifts for other 2,2’-bis(indolyl)methanes [24].

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The molecular structure of 1 was further confirmed by X-ray crystallography (Figure 1).

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Bond distances and angles within the indolyl moieties are unremarkable and compare favorably

with those reported for related bis(indolyl)methanes [24]. We do note, however, that the

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N(2)−H···N(3) distance of 2.06(2) Å and the relative orientation of the pyridyl moiety and the

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N(2)-containing indolyl moiety confirm the presence of N−H···N hydrogen bonding in the solid
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state [24].
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Figure 1. ORTEP diagram of 1. Thermal ellipsoids are drawn at the 50% probability level.
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Hydrogen atoms, except for those attached to indole nitrogen atoms, are omitted for clarity.
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Selected bond distances (Å) and angles (°): N(1)−H, 0.90(2); N(2)−H, 0.90(2); N(1)−H···N(3),
2.81(2); N(2)−H···N(3), 2.06(2); C(2)–C(1)–C(11), 108.29(14); C(2)–C(1)–C(21), 115.11(16);
C(11)–C(1)–C(21), 113.89(15).

2.2. Tripodal complexes. Reactions of 1 with a slight excess of trimethylaluminum,

triethylaluminum, or tri-iso-butylaluminum at room temperature yielded 2a, 2b, and 2c as light

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R
Al
NH toluene N
N N
+ xs R3Al (1)
20 oC, 15h
N NH
H

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2a M = Al, R = Me
2b M = Al, R = Et
1 2c M = Al, R = iBu

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green to yellow solids in yields of 91%, 72%, and 47%, respectively (eq 1). Yields decreased with

increased steric bulk of the alkyl substituent on aluminum so much that reactions of 1 with tBu3Al

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or tBu3Ga were very sluggish at room temperature and required refluxing in toluene for 20 hours

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to afford 2d and 3 as yellow solids in low isolated yields of only 19% and 10%, respectively (eq
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2). Side-products were observed in all cases and product distributions were dependent on the

reaction stoichiometry and reaction conditions as will be discussed below.

M

t
Bu
M
NH
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t toluene N N
+ 2 Bu3M N (2)
reflux, 20h
N NH
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2d M = Al
1 3 M = Ga
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1
H NMR spectra of 2a-2d and 3 are similar and consistent with the proposed structures of
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Cs symmetry. The 1H NMR spectrum for each compound exhibits two triplets in the aromatic
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region assigned to indole H5 and H6 and two doublet resonances assigned to indole H4 and H7,

respectively, for the two chemically equivalent indolyl moieties. Pyridyl resonances are well

resolved in most spectra. A singlet is observed in the range of 5.97−5.93 ppm for the methine

proton and one singlet is observed in the range of 2.46−2.43 ppm for the indole methyl groups.

Integration confirms the presence of one alkyl group on aluminum in each complex, which is
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consistent with the absence of a downfield broad resonance at or near 9.07 ppm for the NH

protons of the starting ligand. The resonance for the methyl attached to aluminum in 2a appears

upfield at 0.41 ppm as is typical for Al−CH3 groups. For example, Wang and coworkers [25]

reported chemical shifts at −0.12 and 0.02 ppm for the methyl group in the two isomers of Al(7-

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azain)2(7-azain-H)(CH3), where 7-azain is monodentate 7-azaindolyl ligand. The resonance for

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the methylene protons of the Al−CH2CH3 group in 2b appears as a quartet and is also shifted

upfield to 1.13 ppm due to coordination to aluminum. Similarly, the doublet resonance for the

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methylene protons of the Al−CH2CH(CH3)2 group in 2c is shifted slightly upfield to 1.25 ppm.

Singlets are observed at 1.70 ppm and 1.83 ppm for Al−C(CH3)3 and Ga−C(CH3)3 groups in 2d

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and 3, respectively. 2D-COSY experiments resulted in cross peaks that confirm the atom
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connectivity within the ligand, and 13C NMR spectra support the structures proposed on the basis

of 1H NMR data.
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Since the presence of three-coordinate aluminum or gallium in 2a-3 is unlikely based on

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known chemistry of the group 13 elements, and since there is no spectroscopic evidence for a
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fourth donor except for the pyridyl residue of 1, we conclude that 1 acts as a tridentate ligand with

the pyridyl moiety coordinated to aluminum in 2a-2d and gallium in 3. This is supported by the
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results of 2D-NOESY experiments on 2a, which allowed determination of spatial proximity of

hydrogens via through-space coupling information. Cross peaks were evident between the
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aluminum methyl resonance at 0.41 ppm and both the pyridyl H8 resonance at 8.43 ppm and

indolyl H7 resonance at 7.41 ppm. Moreover there is a cross peak between the methine resonance

at 5.93 ppm and pyridyl H11 resonance at 7.69 ppm. These NOESY results are indicative of a

rigidly held, coordinated pyridyl ring in solution.

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Figure 2. ORTEP diagram of one independent molecule of 2b. Thermal ellipsoids are drawn at

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the 50% probability level. Hydrogen atoms are omitted for clarity. Selected bond distances (Å)

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and angles (°): Al(1)−N(11), 1.841(8) ; Al(1)−N(12), 1.859(8) ; Al(1)−N(13), 1.968(7) ;
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Al(1)−C(130), 1.939(10); N(11)−Al(1)−N(12), 98.9(4); N(11)−Al(1)−N(13), 94.2(3);

N(12)−Al(1)−N(13), 92.5(3); N(11)−Al(1)−C(130), 125.0(4); N(12)−Al(1)−C(130), 121.7(4);

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N(13)−Al(1)−C(130), 117.1(4).
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The solid-state structure of 2b•0.25C6H6 was determined by X-ray crystallography (Figure

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2). The asymmetric unit contains a benzene solvate molecule and four independent molecules of

2b, one of which was refined with a disordered N-indolide moiety. Each crystallographically
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independent molecule of 2b consists of a pseudo-tetrahedral aluminum ligated by the pyridyl and

two N-indolide groups from deprotonated 1 to form three six-membered chelate rings. An ethyl
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group completes the coordination sphere of aluminum. The Al−Nindolide distances average 1.856 Å
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and are similar to the terminal Al−Nindolide distances reported for {N,N’-2-

(diethylamino)methylindolide}AlCH3 (1.8779(15) Å, 1.8879(14) Å) [26a], indolylaldiminato

complexes [2-(RN=CH)C8H5N]AlR’2 (R = tBu, R’ = Me (1.882(2) Å); R = 2,6-Me2C6H3, R’ = Et

(1.910(2) Å)) [26b] and Al(7-azain)2(7-azain-H)(CH3) (1.868(2) Å − 1.882(2) Å) [25a], as well as

the average Al−Npyrrolide distances of 1.825 Å reported for (N-pyrrolide)3(Me2NH)Al [27]. The
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Al−Npyridyl distances average 1.976 Å indicative of a dative bond between the neutral pyridyl

donor and aluminum [28].

2.3. Bidentate coordination mode. As noted above, refluxing conditions were required to

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produce only modest yields of 2d and 3. Depending on reaction stoichiometry, reaction of 1 with
t
Bu3Al yielded a mixture of 2d and another compound identified as 4. Similarly, compound 5

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was identified as the major side-product in the reaction of tBu3Ga with 1 under refluxing

conditions. A 2:1 ratio of tBu3M (M = Al, Ga) to 1 improved isolated yields of 2d and 3, which

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remain low. Further investigation revealed that when reactions were conducted with an

equimolar ratio of tBu3M to 1, complexes 4 and 5 were obtained as yellow solids in greater than

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45% yield (eq 3). These complexes, in which mono-deprotonated 1 adopts a bidentate

coordination mode, can be viewed as intermediates en route to the formation of tripodal

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complexes 2a-3 in which di-deprotonated 1 adopts a tridentate coordination mode. However,

reactions at higher temperatures did not convert complex 4 to 2d or complex 5 to 3, suggesting an

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alternate pathway to the formation of the tripodal complexes.

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NH N t
toluene Bu
+ tBu3M M (3)
reflux, 20h t
N NH N N Bu
H
C

4 M = Al
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1 5 M = Ga

The NMR spectra of 4 and 5 indicate structures of C1 symmetry. The 1H NMR spectrum

of 4 in CDCl3 exhibits two distinct sets of resonances for protons on two chemically inequivalent

indolide moieties, including two singlets at 2.57 ppm and 2.24 ppm, each corresponding to a

chemically inequivalent methyl group on the two indolides. A broad resonance at 7.82 ppm
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integrating to one proton indicates that one of the indolyl rings retains the NH proton and is not

coordinated to aluminum. The doublet resonance at 7.80 ppm corresponding to H7 of the

coordinated N-indolide group is shifted downfield relative to the doublet resonance at 7.45 ppm

for H7 of the free, protonated indolide group. This is consistent with our previous observations

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that indolyl H7 resonances are shifted downfield in indolyl phosphines and even further shifted

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downfield upon coordination of the indolylphosphine to a metal [12g,12h]. The aliphatic region

of the 1H NMR spectrum also exhibits a singlet methine resonance at 6.32 ppm and two singlet

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resonances at 1.32 ppm and 0.52 ppm, each integrating to nine protons and assigned to the two

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M
D
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Figure 3. ORTEP diagram of 4. Thermal ellipsoids are drawn at the 50% probability level.
C

Hydrogen atoms, except for indole NH atoms, are omitted for clarity. Selected bond distances
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(Å) and angles (°): Al(1)–N(1),1.884(2); Al(1)–N(3), 2.009(2); Al(1)−C(31), 2.015(3);

Al(1)−C(41), 2.012(3); N(1)–Al(1)–N(3), 95.06(10); N(1)–Al(1)–C(31), 109.20(11); N(1)–Al(1)–

C(41), 114.69(11); N(3)–Al(1)–C(31), 101.41(11); N(3)–Al(1)–C(41), 110.72(11); C(31)–Al(1)–

C(41), 121.63(12).
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13
chemically inequivalent tert-butyl groups on the aluminum. The C NMR spectrum of 4

supports the proposed structure.

The molecular structure of 4, as determined by X-ray crystallography (Figure 3), confirms

the structure proposed on the basis of NMR spectroscopic data. One of the indole groups of 1 is

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deprotonated and coordinated to aluminum to form, along with the coordinated pyridyl group, a

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six-membered chelate ring. The other indole group remains protonated and uncoordinated. The

aluminum is approximately tetrahedral with angles ranging from 95.06(10)° to 121.63(12)°. The

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Al−Nindolide distance is 1.884(2) Å, and the Al−Npyridyl distance is 2.009(2) Å. These are

comparable to the Al−Nindolide and Al−Npyridyl distances for 2b•0.25C6H6.

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2.4. Bimetallic complexes. Although formation of tripodal complexes 2a and 2b was
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facilitated by using a slight excess of trialkylaluminum, a side-product was observed by 1H NMR
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spectroscopy as the amount of excess trialkylaluminum increased. This side-product became the

dominate product as the trialkylaluminum to ligand ratio approached 2:1. Reactions of 1 with two
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equivalents of Me3Al or Et3Al afforded bimetallic complexes 6a and 6b as bright yellow solids in
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64% and 58% yield, respectively (eq 4).

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R R
N R
NH toluene R Al Al
+ 2 R3Al N (4)
o
20 C, 2h N
C

N NH
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6a R = Me
1 6b R = Et

The structures for 6a and 6b were not immediately evident from NMR spectroscopy. The

room-temperature 1H NMR spectrum of 6a in CDCl3 consists of relatively sharp resonances for

the coordinated pyridyl moiety (doublets at 8.30 and 7.87 ppm; triplets at 7.99 and 7.45 ppm),
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two sets of broad 3-methylindolide aromatic resonances, and two broad 3-methylindolide methyl

resonances at 2.62 and 2.36 ppm, indicative of two chemically inequivalent 3-methylindolide

moieties at room temperature. The presence of four resonances upfield of TMS, each of which

integrated to three protons, is indicative of four aluminum-bound methyl groups. The two methyl

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resonances at −0.46 and −1.73 ppm are sharp suggesting that they are rigidly bound to aluminum,

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but the two aluminum-bound methyl resonances at −0.23 and −1.83 ppm are broad at room

temperature indicating a dynamic exchange process on the NMR timescale. 1H NMR spectra

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below −5 °C display sharp, resolved peaks.

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A NOESY experiment was helpful in assigning relative spatial arrangement of the
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different groups in 6a. The resonance at 8.30 ppm for pyridyl H8 has cross peaks with the two

broad aluminum-bound methyl resonances at −0.23 ppm and −1.83 ppm and a much weaker cross
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peak with the sharp aluminum-bound methyl resonance at −0.46 ppm. There was no cross peak

for H8 and the sharp aluminum-bound methyl resonance at −1.73 ppm. These data indicate that
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H8 is nearest to the aluminum-bound methyl protons involved in the dynamic exchange process
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with resonances at −0.23 ppm and −1.83 ppm, and furthest from the methyl protons that exhibit

resonances at −0.46 ppm and −1.73 ppm. In addition, the strong cross peak between pyridyl H11
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and the methine proton, and the two weaker cross peaks for H11 interacting with the indolyl

methyl protons, indicate that the pyridyl moiety is coordinated and that the structure is fairly rigid
C
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at room temperature.

To learn more about the dynamic exchange process observed for 6a, and to calculate the

activation energy for this process, variable-temperature 1H NMR spectra were obtained in CDCl3

and in toluene-d8 (Figure 4). At the slow exchange limit (−20 °C, Figure 4) all four aluminum-

bound methyl peaks are sharp, well-resolved, and of equal intensity. At higher temperature, the
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outer two methyl resonances decrease in intensity, broaden, and shift towards each other while the

inner two resonances remain sharp at all temperatures. Coalescence of the two broad aluminum-

bound methyl resonances takes place between 60 °C and 70 °C. Using data for the coalescence of

the aluminum-bound methyl resonances, the activation energy (∆Gc‡) for this exchange process

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was calculated to be 15.1 (± 0.1) kcal/mol [29]. The activation energy was also calculated based

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on analysis of the indolide methyl resonances in CDCl3. At the slow exchange limit, the two

indolide methyl resonances are sharp and well-resolved at 2.64 and 2.37 ppm. The two

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resonances coalesce between 50 °C and 55 °C. Using this data, ∆Gc‡ was calculated to be 15.5 (±

0.1) kcal/mol, which is comparable to the activation energy calculated based on the coalescence

of the aluminum-bound methyl resonances.

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M
D
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C EP
AC

Figure 4. Aluminum-bound methyl region of variable-temperature 1H NMR spectra of 6a in

toluene-d8 from −20 to 90 °C. Spectra were obtained at 400 MHz.

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MeC MeA,B
MeC
Me A
MeB
N MeD py N
Al
MeA,B MeD N
MeB Al Al Al Al MeA
C N
N N Me N
N Al
MeD

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6a 7 6a

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Scheme 2. Proposed mechanism for the dynamic exchange process observed for compound 6a.

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We propose (Scheme 2) that the dynamic exchange process involves dissociation of

pyridine from aluminum, formation of a bimetallic intermediate 7 with two bridging N-indolides,

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and subsequent coordination of pyridine to aluminum to reform 6a. All steps are proposed to be
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reversible. The proposed intermediate is symmetric and accounts for the interconversion of the

two 3-methylindolide groups at higher temperatures. Similarly, dissociation of pyridine from

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aluminum allows rotation around the Al−Nindolide bond for the three-coordinate aluminum and
D

results in scrambling of the methyl groups labeled MeA and MeB. Coordination of pyridine must
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occur at the aluminum ligated by MeA and MeB. Steric constraints prevent the AlMeCMeD moiety

from being attacked by the pyridine group. The AlMeCMeD moiety remains coordinated by one
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terminal N-indolide and one bridging N-indolide or two bridging N-indolides throughout the

exchange process, and the two aluminum centers do not exchange on the NMR timescale at the
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temperatures investigated. Thus, the 1H NMR resonances for MeC and MeD remain sharp from
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−20 to 90 °C. This is consistent with the NOESY results and we assign resonances at −0.46 ppm

and −1.73 ppm to MeC and MeD protons, respectively. In further support of this mechanism, we

previously reported the synthesis and characterization of [{bis(N-3-

methylindolyl)phenylmethane}(AlMe2)2] (8) by NMR spectroscopy and X-ray crystallography

 ACCEPTED MANUSCRIPT

Me
Al
Ph N Me
H N Me
Al

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Me

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Figure 5. Line drawing (left) and molecular structure (right) of previously reported 8.12e

U SC
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M
D
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Figure 6. ORTEP diagram of 6a. Thermal ellipsoids are drawn at the 50% probability level.

Hydrogen atoms are omitted for clarity. Selected bond distances (Å) and angles (°): Al(1)–N(1),
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1.885(2); Al(1)–N(2), 2.022(2); Al(2)–N(2), 1.969(2); Al(2)–N(3), 1.968(2); Al(1)–C(41),

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1.954(3); Al(1)–C(42), 1.965(3); Al(2)–C(31), 1.954(3); Al(2)–C(32), 1.959(3); N(2)–Al(1)–

N(1), 98.78(9); N(1)–Al(1)–C(41), 109.46(13); N(1)–Al(1)–C(42), 109.14(14); N(2)–Al(1)–

C(41), 105.99(13); N(2)–Al(1)–C(42), 110.85(12); N(2)–Al(2)–C(31), 112.84(12); N(2)–Al(2)–

C(32), 114.28(11); N(3)–Al(2)–C(31), 106.66(13); N(3)–Al(2)–C(32), 109.00(12); C(31)–Al(2)–

C(32), 117.32(14); N(3)–Al(2)–N(2), 93.70(9); Al(2)–N(2)–Al(1), 123.35(10).

 ACCEPTED MANUSCRIPT

(Figure 5) [12e]. Compound 8 is analogous to the proposed intermediate 7 except that there is a

non-coordinating phenyl group attached to the methine carbon in 8 rather than a pyridyl group

attached to the methine carbon as in 6a and 7.

X-ray crystallography confirmed the presence of a bridging µ2-η1:η1-N-indolide in the

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solid-state structure of 6a•C7H8 as shown in Figure 6. The two AlMe2 moieties are bridged by a

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3-methylindolide group from deprotonated 1, and the coordination spheres of Al(1) and Al(2) are

completed by a terminal N-indolide and the pyridine group, respectively. Each aluminum atom is

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approximately tetrahedral. The bridging Al–Nindolide distances of 2.022(2) Å and 1.969(2) Å are

elongated compared to the terminal Al–Nindolide distances of 1.885(2) Å in 6a•C7H8, 1.845(6) Å

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and 1.870(6) Å in 2b•0.25C6H6, and 1.884(2) Å in 4. The elongated Al−Nindolide distances for the
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bridging 3-methylindolides are comparable to those previously reported for related aluminum

complexes [12e].
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Spectroscopic data indicate that the structure of complex 6b is analogous to that for 6a.
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The aromatic region of the 1H NMR spectrum of 6b exhibits resonances for two chemically
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inequivalent 3-methylindolide groups, and the aliphatic region shows singlets at 2.64 ppm and

2.35 ppm corresponding to the 3-methylindolide methyl groups. Resonances are sharp at room-
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temperature. Resonances for the four inequivalent ethyl groups on aluminum are as expected for

an ABX3 spin system. Triplets integrating to three protons each are observed at 1.17 ppm, 0.97
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ppm, 0.11 ppm and –0.13 ppm for the methyl protons, and the eight methylene protons of the
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ethyl groups are diastereotopic (AB portion of the ABX3 spin system) and appear as distinct

multiplets at 0.66 ppm, 0.47 ppm, 0.32 ppm, 0.05 ppm, –0.78 ppm, –0.92 ppm, –0.99 ppm and –

1.22 ppm. The upfield shifts of the methylene protons are as expected for aluminum-bound ethyl
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groups. The 13C NMR spectrum of 6b is consistent with the assignments in the 1H NMR

spectrum and supports the proposed structure.

2.5. Attempts to prepare cationic tripodal complexes. Cationic complexes of aluminum

supported by nitrogen donor ligands have previously been prepared by abstraction of hydride or

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alkide from an organoaluminum complex [8a,9,15,30,31]. Tris(pentafluorophenyl)borane and

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triphenylcarbenium, dimethylanilinium and acid etherate salts that contain a bulky, non-

coordinating borate anion have been shown to be effective abstraction reagents. For example,

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Jordan and coworkers [30] isolated a three-coordinate cationic β-diketiminate complex of

aluminum via a methide abstraction strategy using [Ph3C][B(C6F5)4] (eq 5).

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Ar Ar
N + [Ph3C][B(C6F5)4] N
Me
Al Al Me [B(C6F5)4] (5)
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- Ph3CMe
N Me N
Ar Ar
Ar = 2,6-iPr2C6H3
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In another example, Gibson and coworkers [15] unsuccessfully attempted to isolate a

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cationic aluminum complex from LAlMe2 (L= a bulky carbazolyl ligand) by methide abstraction

with [Ph3C][B(C6F5)4], but only obtained decomposition products. However, reaction of the same
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complex with [H(OEt2)][TFPB] ([TFPB] = [B{3,5-(CF3)2C6H3}4]–) resulted in the short-lived

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complex [LAlMe(OEt2)]+ which decomposed by transfer of one aryl group from the borate anion

to aluminum.

Similarly, Dagorne and coworkers [31] were able to generate a short-lived cationic

complex using B(C6F5)3 to abstract methide from a bis(oxazolinato) complex of aluminum. They
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were able to isolate and characterize a more stable abstraction product in the presence of a

coordinating Lewis base such as THF and Me2NPh (eq 6).

O O
N + B(C6F5)3 N
Me L

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Al Al [MeB(C6F5)3] (6)
+L
N Me N Me
O O

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L = THF, Me2NPh

Our preliminary attempts to obtain and characterize cationic complexes by abstraction of

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hydride or alkide from 2a-2d were unsuccessful. Mixing toluene solutions of 2a and

[Ph3C][TFPB] at room temperature, followed by stirring, resulted in phase separation to give oily,

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sticky residues. Solvents were removed under vacuum and a singlet at 5.55 ppm in the 1H NMR
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spectrum of the residue indicated formation of triphenylmethane, apparently the result of hydride
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abstraction. Similar results were obtained for reactions of [Ph3C][TFPB] or [Ph3C][B(C6F5)4] with

2b, 2c or 2d. Phase separation of an oily residue from an aromatic solvent can be indicative of
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clathrate formation upon generation of cationic aluminum complexes with bulky anions [30], but
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1
H NMR spectroscopy showed only the presence of Ph3CH and a very complicated mixture of

unidentified compounds. We found no evidence for the formation of stable, cationic complexes.
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We can only hypothesize that hydride was abstracted from the ligand and/or the alkyl (for 2b-2d),

and that any cationic aluminum complexes that may have been generated quickly decomposed by
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aryl transfer from the borate salt to aluminum and/or by other pathways.
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Abstraction of hydride from a coordinated ligand and free ligand has been observed

previously. Dagorne and coworkers [31] reported a resonance stabilized cationic aluminum

complex (eq 7) resulting from hydride abstraction from a methyl group on the backbone of the

ligand while the methyl groups on aluminum remained intact. We also note that Pindur and
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O O
N + [Ph3C][B(C6F5)4] N
Me Me
Al Al [B(C6F5)4] (7)
Me - Ph3CH
N N Me
O O

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coworkers [32] observed that reaction of a tris(indolyl)methane with [Ph3C][BF4] resulted in

abstraction of the methine hydrogen or decomposition of the ligand, depending on the

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substituents on the indolyl groups.

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We anticipated that abstraction of the methine proton from coordinated 1 could be avoided

using dimethylanilinium and etherate acid salts. Unfortunately, all reactions of 2a-2d with

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[H(OEt2)][TFPB] or [HNMe2Ph][B(C6F5)4] in diethyl ether, THF or CDCl3 led to alkane
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elimination, a complicated mixture of unidentified products, and in many cases, protonated ligand

[1•H][TFPB] or [1•H][ B(C6F5)4].

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D

3. Conclusions

We have successfully synthesized a new diamidoamine ligand, bis(3-methylindolyl)-2-

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pyridylmethane (1), and demonstrated bidentate, tridentate, and bridging N-indolide coordination
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modes for deprotonated 1 in seven new complexes of aluminum and two of gallium.

Diamidoamines are popular ligands [33] for modifying the chemistry of main group metals [34],
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transition metals [35], and even actinides [36]. Bis(3-methylindolyl)-2-pyridylmethane and

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analogs with a variety of substituents on the indole ring and a range of possible nitrogen donor

groups will be useful additions to the class of diamidoamine ligands for use in inorganic and

organometallic chemistry.
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4. Experimental Section

4.1. General procedures

All reactions were performed under an atmosphere of purified nitrogen using standard

inert atmosphere techniques. Hexanes, pentane, and acetonitrile were distilled from calcium

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hydride, and toluene was distilled from sodium prior to use. Chloroform-d and benzene-d6 were

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dried by storage over activated molecular sieves. Toluene-d8 and DMSO-d6 were used as

received. Trimethylaluminum, triethylaluminum, tri-iso-butylaluminum, 3-methylindole, 2-

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pyridinecarboxaldehyde, Amberlite IRA-67 ion exchange resin, and anhydrous aluminum

chloride were purchased from Aldrich Chemical. B(C6F5)3 and LiB(C6F5)4 were purchased from

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Boulder Scientific and used without further purification. Tri-tert-butylaluminum was prepared by
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modification of the procedures reported by Lehmkuhl [37] and Uhl [38]. Tri-tert-butylgallium

was prepared using the procedure reported by Kovar and co-workers [39]. The
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triphenylcarbenium salt [Ph3C][TFPB] [40] and the acid etherate salt [H(OEt2)2][TFPB] [41] were
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prepared by published procedures. The triphenylcarbenium salt [Ph3C][B(C6F5)4] was prepared by

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reaction of [Ph3C][OTf] [42] and LiB(C6F5)4, and the dimethylanilinium salt [HNMe2Ph][TFPB]

was prepared by reaction of [HNMe2Ph]Cl [43] and NaTFPB [40]. Solution NMR spectra were
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recorded on a Varian Unity 400 MHz or Varian Inova 600 MHz spectrometer. Two-dimensional

NMR spectra were obtained on a Varian Inova 600 spectrometer. Chemical shifts are reported
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relative to tetramethylsilane. Some of the 13C NMR assignments are tentative and based on
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previously reported NMR assignments for diindolylmethanes [24,44], as well as NMR

assignments of indole derivatives reported by Park [45]. The numbering scheme for the pyridyl

and indole rings of compound 1 below to aid discussion of NMR data and assignment of

resonances. Elemental analyses were performed by Schwarzkopf Microanalytical Laboratories,

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Woodside, NY. Results for carbon analyses were generally 1-2% lower than calculated. We and

others have previously noted lower than expected carbon analyses for some organoaluminum

compounds [46]. For example, Shapiro and coworkers [46b] reported low carbon analyses for

Cp3Al•C≡NtBu and attributed this discrepancy to formation of aluminum carbides in the

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combustion analyses. High-resolution mass spectrometric analyses (TOF ES) were provided by

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the Mass Spectrometry and Proteomics Facility at The Ohio State University.

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4.2. Synthesis of bis(3-methylindol-2-yl)-2-pyridylmethane (1)

2-Pyridinecarboxyaldehyde (2.80 mL, 29.4 mmol) was added via syringe to a stirred,

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colorless solution of 3-methylindole (7.52 g, 57.3 mmol) in 100 mL of ethanol. A yellow solution
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formed. Concentrated sulfuric acid was added (20 drops). The resulting orange solution was

refluxed for 20 hours. Methylene chloride (40 mL) was added and the solution was stirred at 0 °C
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for 1 hour. A bright yellow solid ([1d•H][HSO4]) (6.37 g, 49%) precipitated and was collected by
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filtration. NMR data for ([1d•H][HSO4]). 1H NMR (DMSO-d6, 400 MHz): δ 10.59 (s, 2H, NH),
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8.70 (br d, 3JHH = 4.4, 1H, pyridyl H8 ), 8.06 (br, 1H, pyridyl H9), 7.57 (br, 1H, pyridyl H10),

7.59 (d, 3JHH = 8.0 Hz 1H, pyridyl H11), 7.43 (t, 3JHH = 8.0 Hz, 2H, indolyl H7 ), 7.31 (t, 3JHH =
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8.0 Hz, 2H, indolyl H4 ), 7.03 (t, 3JHH = 7.2 Hz, 2H, indolyl H6 ), 6.97 (t, 3JHH = 7.2 Hz, 2H,

indolyl H5 ), 6.26 (s, 1H, CH), 2.14 (s, 6H, CH3). 13C{1H} NMR (DMSO-d6, 100.6 MHz): 157.85
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(s, pyridyl-ipso, br), 146.63 (s, pyridyl C8, br), 141.06 (s, pyridyl C9, br), 135.68 (s, C7a), 132.12
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(s, C2, br), 128.33 (s, C3a), 124.73 (s, pyridyl C10, br), 123.49 (s, pyridyl C11, br), 121.03 (s,

C5), 118.42 (s, C6), 118.05 (s, C4), 111.19 (s, C7), 107.23 (s, C3), 41.20 (s, CH), 8.35 (s, CH3).

Deprotonation of [1•H][HSO4 ] to afford free base 1 was accomplished using Amberlite.

Amberlite IRA-67 (30 mL, 48 meq.) was added to a stirred suspension of [1•H][HSO4 ] (4.3 g,
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0.024 mol) in 100 mL of acetonitrile and the mixture was stirred at 25 °C under nitrogen flow for

1 h resulting in a clear yellow solution. The Amberlite was filtered off and solvent was removed

from the filtrate in vacuo resulting in a powdery, yellow solid 1. Yield: 3.2 g, 94%. 1H NMR

(CDCl3, 600 MHz): δ 9.05 (s, 2H, NH), 8.69 (d, 3JHH = 4.8 Hz, 1H, pyridyl H8), 7.68 (t, 3JHH =

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7.8 Hz, 1H, pyridyl H9), 7.49 (d, 3JHH = 7.8 Hz, 2H, indolyl H7), 7.43 (d, 3JHH = 7.8 Hz, 1H,

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pyridyl H11), 7.29 (d, 3JHH = 7.8 Hz, 2H, indolyl H4), 7.22 (t, 3JHH = 7.4 Hz, 1H, pyridyl H10),

7.11 (t, 3JHH = 7.5 Hz, 2H, indolyl H5), 7.06 (t, 3JHH = 7.5 Hz, 2H, indolyl H6), 5.93 (s, 1H, CH),

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13
2.32 (s, 6H, CH3). C{1H} NMR (CDCl3, 100.6 MHz): δ 159.87 (s, pyridyl-ipso), 149.67 (s,

pyridyl C8), 137.60 (s, pyridyl C9), 135.36 (s, indolyl C7a), 133.10 (s, indolyl C2), 128.97 (s,

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indolyl C3a), 123.64 (s, pyridyl C10), 122.20 (s, pyridyl C11), 121.55 (s, indolyl C5), 119.12 (s,
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indolyl C6), 118.42 (s, indolyl C7), 110.86 (s, indolyl C4), 107.40 (s, indolyl C3), 41.61 (s, CH),

8.64 (s, CH3). HRMS (ES) m/z for C24H22N3 (M+H+): calcd, 352.1813; found, 352.1815. Anal.
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calcd for C24H21N3: C, 82.01; H, 6.02; N, 11.95. Found: C, 82.07; H, 6.11; N, 11.51.
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4.3. Synthesis of (2-C5H4N)HC(3-CH3C8H4N)2AlCH3 (2a)

To a stirred solution of bis(3-methylindol-2-yl)-2-pyridylmethane (1, 0.828 g, 2.35 mmol) in

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freshly distilled toluene (15 mL), excess trimethyl aluminum (1.50 mL, 3.00 mmol, 2.0 M toluene

solution) was added via syringe. An immediate color change from orange to black green was
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noticed. The resulting mixture was stirred at room temperature for 15 hours. The solution was
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then reduced to 5 mL in volume and 20 mL of freshly distilled hexanes was added. A light green

solid was precipitated and collected on a medium frit and washed with (3 × 1 mL) hexanes and

dried under vacuum for 2 hours. Yield: 0.878 g, 2.14 mmol, 91%. 1H NMR (CDCl3, 400 MHz): δ

8.42 (d, 3JHH = 4.8 Hz, 1H, pyridyl H8), 7.89 (t, 3JHH = 7.8 Hz, 1H, pyridyl H10), 7.70 (d, 3JHH =
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7.6, 1H, pyridyl H11), 7.40 (m, 4H, indolyl H7, H4), 7.34 (t, 3JHH = 7.8 Hz, 1H, pyridyl H9), 7.05

(t, 3JHH = 7.6 Hz, 2H, indolyl H6), 6.98 (t, 3JHH = 7.4 Hz, 2H, indolyl H5), 5.94 (s, 1H, CH), 2.44

(s, 6H, CH3), 0.41 (s, 3H, AlCH3). 13C{1H} NMR (CDCl3, 100.6 MHz): δ 161.20 (s, pyridyl-

ipso), 145.08 (s, pyridyl C8), 142.47 (s, pyridyl C9), 141.87 (s, C7a), 137.76 (s, C2), 130.61 (s,

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C3a), 124.03 (s, pyridyl C10), 122.80 (s, pyridyl C11), 120.85 (s, C5), 118.49 (s, C6), 118.27 (s,

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C4), 113.13 (s, C7), 107.67 (s, C3), 41.56 (s, CH), 8.80 (s, CH3). Anal. calcd for C25H22N3Al: C,

76.95; H, 5.96; N, 10.36. Found: C, 74.07; H, 6.02; N, 10.15.

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4.4. Synthesis of (2-C5H4N)HC(3-CH3C8H4N)2AlC2H5 (2b)

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To a stirred solution of di(3-methylindol-2-yl)-2-pyridylmethane (0.890 g, 2.53 mmol) in
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freshly distilled toluene (15 mL), excess triethylaluminum (1.60 mL, 3.04 mmol, 1.9 M toluene

solution) was added via syringe. An immediate color change from orange to black green was
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noticed. The resulting mixture was stirred at room temperature for 15 h. The product would
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occasionally precipitate out of solution at this point. The reaction mixture was then reduced to 5
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mL in volume and freshly distilled hexanes (20 mL) were added. A light green solid precipitated,

was collected on a medium frit and washed with hexanes (3 × 1 mL) prior to drying under
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vacuum for 2 hours. Yield: 0.742 g, 1.82 mmol, 72%. 1H NMR (CDCl3, 400 MHz): δ 8.44 (d,
3
JHH = 8.0, 1H, pyridyl H8), 7.89 (t, 3JHH = 7.8 Hz, 1H, pyridyl H10), 7.69 (d, 3JHH = 8.0 Hz, 1H,
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pyridyl H11), 7.40 (m, 4H, indolyl H4, H7), 7.34 (t, 3JHH = 7.8 Hz, 1H, pyridyl H9), 7.08 (t, 3JHH
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= 7.6 Hz, 2H, indolyl H6), 6.98 (t, 3JHH = 7.6 Hz, 2H, indolyl H5), 5.93 (s, 1H, CH), 2.43 (s, 6H,

CH3), 1.71 (t, 3JHH = 8.4 Hz, 3H, AlCH2CH3), 1.13 (q, 3JHH = 8.4 Hz, 2H, AlCH2CH3). 13C{1H}

NMR (CDCl3, 100.6 MHz): δ 161.32 (s, pyridyl-ipso), 145.12 (s, pyridyl C8), 142.45 (s, pyridyl

C9), 141.87 (s, C7a), 137.82 (s, C2), 130.62 (s, C3a), 124.13 (s, pyridyl C10), 122.81 (s, pyridyl
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C11), 120.92 (s, C5), 118.47 (s, C6), 118.28 (s, C4), 113.30 (s, C7), 107.75 (s, C3), 41.58 (s, CH),

8.79 (s, CH3), 8.46 (s, AlCH2CH3). Anal. calcd for C26H24N3Al: C, 78.20; H, 6.19; N, 9.50.

Found: C, 76.98; H, 6.84; N, 9.76.

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4.5. Synthesis of (2-C5H4N)HC(3-CH3C8H4N)2 Al(CH2)CH(CH3)2 (2c)

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To a stirred solution of bis(3-methylindol-2-yl)-2-pyridylmethane (1, 0.687 g, 1.96 mmol) in

freshly distilled toluene (15 mL) at –78 °C, excess tri-iso-butylaluminum (0.421 g, 2.12 mmol ) in

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15 mL of toluene was added via cannula. An immediate color change to orange was noticed. The

resulting mixture was warmed to room temperature and stirred for 15 hours. The solution was

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then reduced to 5 mL in volume and freshly distilled hexanes (20 mL) were added. A bright
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yellow solid was precipitated and collected on a medium frit and washed with (3 × 1 mL) hexanes
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and dried under vacuum for 2 hours. Yield: 0.40 g, 0.93mmol, 47%. 1H NMR (CDCl3, 400

MHz): δ 8.52 (d, 3JHH = 7.6, 1H, pyridyl H8), 7.89 (t, 3JHH = 7.6 Hz, 1H, pyridyl H10), 7.69 (d,
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3
JHH = 7.6 Hz, 1H, pyridyl H11), 7.47 (d, 3JHH = 8.0 Hz, 2H, indolyl H7), 7.41 (d, 3JHH = 7.6 Hz,
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2H, indolyl H4), 7.35 (t, 3JHH = 7.6 Hz, 1H, pyridyl H9), 7.08 (t, 3JHH = 7.6 Hz, 2H, indolyl H6),

6.98 (t, 3JHH = 7.6 Hz, 2H, indolyl H5), 5.93 (s, 1H, CH), 2.69 (sept, 3JHH = 6.4 Hz, 1H,
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AlCH2CH(CH3)2), 2.43 (s, 6H, CH3), 1.37 (d, 3JHH = 6.4 Hz, 6H, AlCH2CH(CH3)2), 1.25 (d, 3JHH

= 8.0 Hz, 2H, AlCH2CH(CH3)2). 13C{1H} NMR (CDCl3, 100.6 MHz): δ 161.31 (s, pyridyl-ipso),
C

145.32 (s, pyridyl C8), 142.44 (s, pyridyl C9), 141.92 (s, C7a), 137.87 (s, C2), 130.69 (s, C3a),
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124.12 (s, pyridyl C10), 122.77 (s, pyridyl C11), 120.85 (s, C5), 118.45 (s, C6), 118.28 (s, C4),

113.44 (s, C7), 107.70 (s, C3), 41.57 (s, CH), 28.69 (s, AlCH2CH(CH3)2), 26.34 (s,

AlCH2CH(CH3)2), 17.1 (br, AlCH2) 8.79 (s, CH3). Anal. calcd for C28H28N3Al: C, 78.47; H,

6.65; N, 9.06. Found: C, 76.74; H, 6.78; N, 9.33.

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4.6. Synthesis of (2-C5H4N)HC(3-CH3C8H4N)2AlC(CH3)3 (2d)

To a stirred solution of bi(3-methylindolyl)-2-pyridylmethane (1, 0.230 g, 0.654 mmol) in

freshly distilled toluene (15 mL), excess tBu3Al (0.246 g, 1.24mmol) in 10 mL of toluene was

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added via cannula. An immediate color change to light orange was noticed. The resulting mixture

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was refluxed for 20 hours. The solution was then reduced to approximately 3 mL in volume,

freshly distilled pentane (20 mL) was added, and the mixture was chilled to 0 °C. A yellow solid

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precipitated and was collected on medium frit, washed with (3 × 1 mL) pentane and dried under

vacuum for 2 hours. Yield: 0.055 g, 0.125 mmol, 19%. 1H NMR (CDCl3, 400 MHz): δ 8.56 (d,
3

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JHH = 5.6 Hz, 1H, pyridyl H8), 7.95 (t, 3JHH = 7.8 Hz, 1H, pyridyl H10), 7.75 (d, 3JHH = 7.2, 1H,
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pyridyl H11), 7.53 (d, 3JHH = 8.0 Hz, 2H, indolyl H7), 7.40 (t, 3JHH = 7.8 Hz, 1H, pyridyl H9),
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7.43 (d, 3JHH = 6.4 Hz, 2H, indolyl H4), 7.10 (t, 3JHH = 7.6 Hz, 2H, indolyl H6), 7.00 (t, 3JHH = 7.4

Hz, 2H, indolyl H5), 5.97 (s, 1H, CH), 2.44 (s, 6H, CH3), 1.70 (s, 9H, AlC(CH3)3). 13C{1H} NMR
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(CDCl3, 100.6 MHz): δ 161.53 (s, pyridyl-ipso), 145.16(s, pyridyl C8), 142.57 (s, pyridyl C9),
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141.87 (s, C7a), 137.93 (s, C2), 130.78 (s, C3a), 124.46 (s, pyridyl C10), 122.82 (s, pyridyl C11),

121.03 (s, C5), 118.50 (s, C6), 118.35 (s, C4), 113.72 (s, C7), 107.95 (s, C3), 41.53 (s, CH), 29.44
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(s, AlC(CH3)3), 12.27 (br s, AlC(CH3)3), 8.80 (s, CH3).

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4.7. Synthesis of (2-C5H4N)HC(3-CH3C8H4N)2GaC(CH3)3 (3)

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To a stirred solution of 1 (0.24 g, 0.68 mmol) in toluene (15 mL) an excess of two equivalents

of tri-tert-butylgallium (0.340 g, 1.41 mmol) in 15 mL of toluene were added via cannula. An

immediate color change to orange was observed. The resulting mixture was heated under reflux

for 20 h. The solution volume was then reduced to 2-3 mL and hexanes (20 mL) were added. The
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solution was stored at –30 °C overnight. A bright yellow precipitate was obtained and collected

on a medium frit. The 1H NMR spectrum of this solid indicated a mixture of 5 and 3 in

approximate ratio 1:10. The solid was dissolved in hot toluene (10 mL) and kept at –30 °C

overnight. An off-white solid precipitated and was collected on a fine frit and dried under

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vacuum. The 1H NMR spectrum of this solid indicated pure 3. Yield: 0.038 g, 10%. 1H NMR

RI
(CDCl3, 600 MHz): δ 8.48 (d, 3JHH = 5.4 Hz, 1H, pyridyl H8), 7.85 (t, 3JHH = 7.8 Hz, 1H, pyridyl

H10), 7.70 (d, 3JHH = 7.8 Hz, 1H, pyridyl H11), 7.45 (d, 3JHH = 7.2 Hz, 2H, indolyl H7), 7.44 (d,

SC
3
JHH = 7.2 Hz, 2H, indolyl H4), 7.28 (t, 1H, pyridyl H9), 7.08 (t, 3JHH = 7.2 Hz, 2H, indolyl H5),

6.99 (t, 3JHH = 7.2 Hz, 2H, indolyl H6), 5.98 (s, 1H, CH), 2.46 (s, 6H, indolyl CH3), 1.83 (s, 9H,

U
GaC(CH3)3). 13C{1H} NMR (CDCl3, 150.8 MHz): δ 160.69 (s, pyridyl-ipso), 145.67 (s, pyridyl
AN
C8), 141.90 (s, pyridyl C9), 141.60 (s, C7a), 136.87 (s, C2), 130.30 (s, C3a), 125.00 (s, pyridyl
M

C10), 122.60 (s, pyridyl C11), 120.65 (s, C5), 118.52 (s, C6), 117.95 (s, C7), 113.02 (s, C4),

106.81 (s, C3), 41.58 (s, CH), 29.91 (s, GaC(CH3)3), 21.52 (br s, GaC(CH3)3), 8.86 (s, indolyl-
D

CH3).
TE

4.8. Synthesis of (2-C5H4N)HC(3-CH3C8H4N)(3-CH3C8H4NH)Al(C(CH3)3)2 (4)

EP

A solution of tri-tert-butylaluminum (0.282 g, 1.42 mmol) in toluene (15 mL) was added

via cannula to a stirred suspension of 1 (0.500 g, 1.42 mmol) in toluene (15 mL). An immediate
C

color change to orange was observed. The resulting solution was heated under reflux for 20 h.
AC

The solution was then reduced to 2-3 mL in vacuo and hexanes (20 mL) were added. A bright

yellow precipitate was collected on a fine frit and dried under vacuum. Yield: 0.31 g, 45%. 1H

NMR (CDCl3, 400 MHz): δ 8.60 (d, 3JHH = 5.2 Hz, 1H, pyridyl H8), 8.06 (t, 3JHH = 8.0 Hz, 1H,

pyridyl H10), 7.91 (d, 3JHH = 8.0 Hz, 1H, pyridyl H11), 7.82 (s, 1H, NH), 7.80 (d, 3JHH = 8.0 Hz,
 ACCEPTED MANUSCRIPT

1H, bound indolyl H7), 7.58 (t, 3JHH = 7.2 Hz, 1H, pyridyl H9), 7.50 (d, 3JHH = 8.0 Hz, 1H, bound

indolyl H4), 7.46 (d, 3JHH = 8.0 Hz, 1H, free indole H7), 7.18 (t, 3JHH = 8.0 Hz, 1H, bound indolyl

H6), 7.10 (d, 3JHH = 8.0 Hz, 1H, free indole H4), 7.05 – 6.98 (m, 3H, free indole H5, H6, bound

indolyl H5 overlap), 6.32 (s, 1H, CH), 2.57 (s, 3H, CH3), 2.24 (s, 3H, CH3), 1.32 (s, 9H,

PT
C(CH3)3), 0.52 (s, 9H, C(CH3)3). 13C{1H} NMR (CDCl3, 100.6 MHz): δ 161.26 (s, pyridyl-ipso),

RI
146.62 (s, pyridyl C8), 143.42 (s, bound indolyl C3a), 141.79 (s, pyridyl C9), 135.50 (s, free

indole C7a ), 135.17 (s, bound indolyl C2), 134.06 (s, bound indolyl C7a), 131.59 (s, free indole

SC
C2), 128.80 (s, free indole C3a), 127.96 (s, pyridyl C10), 122.62 (s, pyridyl C11), 122.08 (s, free

indole C6), 120.04 (s, bound indolyl C6), 119.32 (s, free indole C6), 118.61 (s, bound indolyl

U
C6), 118.49 (s, free indole C7), 117.86 (s, bound indolyl C7), 115.61 (s, bound indolyl C4),
AN
110.94 (s, free indole C4), 110.73 (s, bound indolyl C3), 105.69 (s, free indole C3), 41.32 (s, CH),

32.26 (s, C(CH3)3), 30.51 (s, C(CH3)3), 16.72 (br s, C(CH3)3), 15.31 (br s, C(CH3)3), 9.52 (s,
M

bound indolyl CH3), 8.88 (s, free indole CH3).

D
TE

4.9. Synthesis of (2-C5H4N)HC(3-CH3C8H4N)(3-CH3C8H4NH)Ga(C(CH3)3)2 (5)

A solution of tri-tert-butylgallium (0.341 g, 1.42 mmol) in toluene (15 mL) was added via
EP

cannula to a stirred suspension of 1 (0.500 g, 1.42 mmol) in toluene (15 mL). The resulting

solution was heated under reflux for 20 h. The solution was then reduced to 2-3 mL and hexanes
C

(20 mL) were added. A bright yellow precipitate was collected on a fine frit. The solid was
AC

recrystallized by dissolving it in a minimum amount of hot toluene (2-3 mL) and adding hot

hexanes (15 mL) until the solution becomes turbid. Hot toluene (0.5 mL) was added until

turbidity disappears. The solution was cooled to 25 °C and stored at –30 °C overnight. A yellow

crystalline solid was isolated by filtration through a fine frit and dried under vacuum. 1H NMR
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(CDCl3, 600 MHz): δ 8.45 (d, 3JHH = 5.4 Hz, 1H, pyridyl H8), 8.07 (br s, 1H, NH), 7.98 (t, 3JHH =

7.8 Hz, 1H, pyridyl H10), 7.87 (d, 3JHH = 7.8 Hz, 1H, pyridyl H11), 7.66 (d, 3JHH = 8.4 Hz, 1H,

bound indolyl H7), 7.52 (d, 3JHH = 7.8 Hz, 1H, bound indolyl H4), 7.46 (dd, 3JHH = 5.4 Hz , 3JHH

= 7.8 Hz, 1H pyridyl H9), 7.42 (d, 3JHH = 7.8 Hz, 1H, free indole H7), 7.14 (t, 3JHH = 7.8 Hz, 1H,

PT
bound indolyl H6), 7.06 (t, 3JHH = 7.2 Hz ,1H, bound indolyl H5), 7.02 – 6.97 (m, 3H, free indole

RI
H5, H6, H4 overlap), 6.23 (s, 1H, CH), 2.48 (s, 3H, CH3), 2.29 (s, 3H, CH3), 1.44 (s, 9H,
13
C(CH3)3), 0.55 (s, 9H, C(CH3)3). C{1H} NMR (CDCl3, 100.6 MHz): δ 160.93 (s, pyridyl-

SC
ipso), 147.63 (s, pyridyl C8), 144.03 (s, bound indolyl C3a), 140.88 (s, pyridyl C9), 136.06 (s,

free indole C7a ), 135.20 (s, bound indolyl C2), 134.26 (s, bound indolyl C7a), 131.22 (s, free

U
indole C2), 128.92 (s, free indole C3a), 127.76 (s, pyridyl C10), 122.47 (s, pyridyl C11), 121.80
AN
(s, free indole C6), 119.64 (s, bound indolyl C6), 119.13 (s, free indole C6), 118.32 (s, bound

indolyl C6), 117.98 (s, free indole C7), 117.90 (s, bound indolyl C7), 115.34 (s, bound indolyl
M

C4), 110.89 (s, free indole C4), 109.89 (s, bound indolyl C3), 105.35 (s, free indole C3), 41.47 (s,
D

CH), 32.18 (s, C(CH3)3), 30.39 (s, C(CH3)3), 24.95 (br s, C(CH3)3), 23.09 (br s, C(CH3)3), 9.42 (s,
TE

bound indolyl CH3), 9.03 (s, free indole CH3).

EP

4.10. Synthesis of (2-C5H4N)HC(3-CH3C8H4N)2Al2(CH3)4 (6a)

Two equivalents of trimethylaluminum (2.00 mL, 4.00 mmol, 2.0 M toluene solution) were
C
AC

added to a stirred solution of 1 (0.7012 g, 2.00 mmol) in freshly distilled toluene (15 mL) via

syringe resulting in an immediate color change from orange to yellow. The resulting mixture was

stirred at 50 °C for two days. The volume of the solution was reduced to 5 mL and distilled

hexane (20 mL) was added. A bright yellow solid precipitated and was collected on medium size

frit, washed with hexanes (3 × 1 mL) and dried under vacuum for 2 h. Yield: 0.578 g, 1.28 mmol,
 ACCEPTED MANUSCRIPT

64 %. 1H NMR (CDCl3, 600 MHz): δ 8.30 (d, 3JHH = 4.8 Hz, 1H, pyridyl H8), 7.99 (t, 3JHH = 7.5

Hz, 1H, pyridyl H10), 7.87 (d, 3JHH = 8.4, 1H, pyridyl H11), 7.74 (br s, 1H, indolyl), 7.53 (br s,

1H, indolyl), 7.48 (br s, 1H, indolyl), 7.43 (t, 3JHH = 6.3 Hz, 1H, pyridyl H9), 7.41 (br s, 1H,

indolyl), 7.36 (br s, 2H, indolyl), 6.99 (br s, 2H, indolyl), 6.24 (s, 1H, CH), 2.62 (br s, 3H, CH3),

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2.36 (br s, 3H, CH3), − 0.23 (br s, 3H, AlCH3), −0.46 (s, 3H, AlCH3), −1.73 (s, 3H, AlCH3),

RI
−1.83 (br s, 3H, AlCH3). 13C{1H} NMR (CDCl3, 100.6 MHz): δ 161.44 (s, pyridyl), 145.27 (br s),

144.43 (s, pyridyl), 142.86 (br s), 142.10 (br s, pyridyl), 139.31 (br s), 136.70 (br s), 136.11 (br s),

SC
131.27 (br s), 127.74 (s), 125.27 (s), 124.70 (br s), 131.20 (br s), 123.57 (s), 120.48 (br s), 119.88

(br s), 117.99 (br s), 117.34 (br s), 113.88 (br s), 105.89 (br s), 41.25 (s, CH), 10.30 (br s, CH3),

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9.39 (br s, CH3), −6.23 (br s, AlCH3), −8.54 (br s, AlCH3), −11.85 (s, AlCH3), −12.67 (br s,
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AlCH3). Anal. calcd for C28H31N3Al2: C, 74.11; H, 7.60; N, 8.00. Found: C, 72.81; H, 7.75; N,

7.96.
M
D

4.11. Synthesis of (2-C5H4N)HC(3-CH3C8H4N)2Al2(C2H5)4 (6b)

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An excess of two equivalents triethylaluminum (0.400 g, 3.50 mmol) in 15 mL of toluene was

added via cannula to a stirred solution of 1 (0.500 g, 1.42 mmol) in toluene (15 mL). An
EP

immediate color change to brownish yellow was observed. The resulting mixture was stirred at 20
C

°C for 2 h. The volume of the solution was reduced to 2-3 mL and then 25 mL of hexanes were
AC

added. The solution was stored at –30 °C overnight. The resulting bright yellow precipitate was

collected on a medium frit. The solid was recrystallized by dissolving in a minimum amount of

hot toluene (2 mL), adding 20 mL of hot hexanes and storing the solution at –30 °C overnight. A

yellow precipitate was collected on a medium frit and dried under vacuum for 5 h. Yield: 0.50 g,

58%. 1H NMR (CDCl3, 600 MHz): δ 8.31 (d, 3JHH = 6.0 Hz, 1H, pyridyl H8), 7.98 (t, 3JHH = 8.4
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Hz, 1H, pyridyl H10), 7.87 (d, 3JHH = 8.4 Hz, 1H, pyridyl H11), 7.83 (d, 3JHH = 7.8 Hz, 1H,

bridging indolyl H7), 7.56 (d, 3JHH = 7.8 Hz, 1H, bound indolyl H7), 7.49–7.38 (m, 5H, bound

indolyl H4, bridging indolyl H5, bound indolyl H6, bridging indolyl H6, pyridyl H9, overlap),

7.02-6.97 (m, 2H, bridging indolyl H4, bound indolyl H5, overlap), 6.22 (s, 1H, CH), 2.64 (s, 3H,

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indolyl CH3), 2.35 (s, 3H, indolyl CH3), 1.17 (t, 3JHH = 8.4 Hz, 3H, CH2CH3), 0.97 (t, 3JHH = 8.4

RI
Hz, 3H, CH2CH3), 0.66 (m, 1H, CH2CH3), 0.46 (m, 1H, CH2CH3), 0.32 (m, 1H, CH2CH3), 0.11

(t, 3JHH = 8.4 Hz, 3H, CH2CH3), 0.04 (m, 1H, CH2CH3), –0.13 (t, 3JHH = 8.4 Hz, 3H, CH2CH3), –

SC
0.77 (m, 1H, CH2CH3), –0.92 (m, 1H, CH2CH3), –0.99 (m, 1H, CH2CH3), –1.22 (m, 1H,

CH2CH3). 13C{1H} NMR (CDCl3, 150.8 MHz): δ 161.57 (s, pyridyl-ipso), 144.87 (s, bound

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indolyl C3a), 144.26 (s, pyridyl C8), 143.20 (s, bridging indolyl C7a), 142.04 (s, pyridyl C9),
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139.78 (s, bridging indolyl C2), 136.98 (s, bridging indolyl C3a), 136.61 (s, bound indolyl C2),

131.13 (s, indolyl bound C7a), 127.91 (s, pyridyl C10), 124.62 (s, bridging indolyl C6), 124.32 (s,
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bound indolyl C6), 123.60 (s, bridging indolyl C3), 123.46 (s, pyridyl C11), 120.42 (s, bridging
D

indolyl C4), 119.83 (s, bound indolyl C7), 117.91 (s, bound indolyl C5), 117.83 (s, bound indolyl
TE

C4), 117.48 (s, bridging indolyl C7), 113.98 (s, bridging indolyl C5), 105.60 (s, bridging indolyl

C3), 41.16 (s, CH), 10.25 (s, CH2CH3), 9.94 (s, CH2CH3), 9.52 (s, bound indolyl CH3), 9.38 (s,
EP

CH2CH3), 8.37 (s, CH2CH3), 7.96 (s, bridging indolyl CH3), 2.57 (br s, CH2CH3), 1.04 (br s,

CH2CH3), –1.30 (br s, CH2CH3), –3.28 (br s, CH2CH3). Anal. Calcd for C32H39N3Al2: C, 73.96;
C

H, 7.56; N, 8.08. Found: C, 71.93; H, 8.04; N, 7.73.

AC

4.12. X-ray crystallography

Crystals of 1 were grown by slow diffusion of hexanes into a toluene solution of 1.

Crystals of 2b•0.25C6H6 were grown from a cold saturated benzene solution. Crystals of 4 were
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obtained from toluene at –30 °C, and crystals of 6a•C7H8 were grown from a toluene/hexane

mixture at –30 °C. X-ray diffraction data were collected on a Siemens three-circle platform

diffractometer equipped with either a 1K CCD detector (1) or a 2K CCD detector (2b•0.25C6H6,

4, 6a•C7H8). The frame data were acquired with the SMART 5.054 [47a] (1) or SMART 5.630

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[47b] (2b•0.25C6H6, 4, 6a•C7H8) software using Mo Kα radiation (λ = 0.71073 Å). Cell constants

RI
were determined with SAINT 6.28A [48a] from the complete dataset. More than a complete

hemisphere was scanned on ω (0.3°) with run times of 60 s/frame for 2b•0.25C6H6 and 45

SC
s/frame for 6a•C7H8, while complete spheres were scanned on ω (0.3°) with run times of 45

s/frame for 4 and 30 s/frame for 1. The frames were integrated using the SAINT 6.28A (1, 4,

U
6a•C7H8) or SAINT 8.35A [48] (2b•0.25C6H6) software and the data were corrected for
AN
absorption and decay using the SADABS [49] program. All structures were solved by direct
M

methods and refined with least-squares refinements on F2 using SHELXTL (v. 5.10 for 1,

2b•0.25C6H6 and v. 6.12 for 4, 6a•C7H8) [50,51]. Final refinements for 2b•0.25C6H6 were
D

performed using SHELXL v. 2017/7 [52]. The asymmetric unit encompasses four independent
TE

molecules of 2b along with a benzene molecule (crystallizing solvent). One of the four

complexes is refined with a disordered indolide ligand (50:50%) and a disordered ethyl group
EP

(65:35%). Disordered carbon and nitrogen atoms were refined with isotropic displacement

parameters. Anisotropic displacement parameters in a second molecule as well as in the benzene

C

molecule show the possibility of more disorder. However, no satisfactory model could be found
AC

and the anisotropic displacement parameters of twelve carbon atoms were restrained to behave

approximately isotropically. The inability to resolve some of the disorder is probably due to the

weak data; no diffraction data could be collected at scattering angles of 2θ > 44° leading to a poor

data/parameter ratio of 5.33. 6a•C7H8 crystallizes with one molecule of toluene in the asymmetric
 ACCEPTED MANUSCRIPT

unit. The methyl carbon of the solvent molecule was restrained to behave approximately

isotropically. Hydrogen atoms were located and refined with isotropic displacement parameters

for 1, calculated on idealized positions for 2b•0.25C6H6 and 4, while a mixed treatment was used

in 6a•C7H8. Details of data collection, solution, and refinement are given in Table 1.

PT
RI
U SC
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M
D
TE
C EP
AC
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Table 1. Crystal data and structure refinement details

_______________________________________________________________________
1 2b•0.25C6H6 4
_______________________________________________________________________

formula C24H21N3 C110H102N12Al4 C32H38N3Al

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fw 351.44 1699.95 491.63
crystal system monoclinic monoclinic monoclinic

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space group P21/c Cc C2/c
a, Å 13.709(2) 13.9477(4) 20.071(5)

SC
b, Å 9.308(2) 34.9394(11) 15.032(4)
c, Å 14.694(2) 19.3071(7) 18.695(4)
α, deg 90 90 90

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ß, deg 108.628(2) 93.993(1) 100.562(7)
γ, deg 90 90 90
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3
V, Å 1776.9(5) 9386.0(5) 5545(2)
Z 4 4 8
3
Dcalcd, g cm¯ 1.314 1.203 1.178
M

T, °C –151 –153 –123

1
µ(Mo Kα), cm¯ 0.78 1.06 0.98
D

λ, Å 0.710 73 0.710 73 0.710 73

transm coeff 0.837–1.00 0.874–1.00 0.845–1.00
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2θ limits, deg 5–55 4–44 3.86–50.0

total no. of data 14069 23855 21627
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no. of unique data 3705 9148 4878

a
no. of obsd data 2910 7377 4016
no. of params/restraints 328/0 1079/74 325/0
C

a,b
R1 0.0549 0.0689 0.0659
a,c
wR2 0.1067 0.1860 0.1271
AC

3
max, min peaks, e/Å 0.184, –0.242 0.718, –0.382 0.370, – 0.257
_________________________________________________________________
a
I > 2σ(I). b R1 = Σ | |Fo| – |Fc| | /Σ |Fo|. c wR2 = [Σ[w (Fo2 – Fc2)2] /Σ[w (Fo2)2]]1/2.
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Table 1. Crystal data and structure refinement details (continued)

__________________________________________________________________
6a•C7H8
__________________________________________________________________

formula C35H39N3Al2

PT
fw 555.65
crystal system monoclinic

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space group P21/c
a, Å 13.4172(17)

SC
b, Å 12.643(2)
c, Å 19.838(3)
α, deg 90

U
ß, deg 108.160(3)
γ, deg 90
AN
3
V, Å 3197.6(7)
Z 4
3
Dcalcd, g cm¯ 1.154
M

T, °C –123
1
µ(Mo Kα), cm¯ 1.18
D

λ, Å 0.710 73
transm coeff 0.910–1.00
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2θ limits, deg 3.88– 50.00

total no. of data 24174
EP

no. of unique data 5621

a
no. of obsd data 4746
no. of params/restraints 461/6
C

a,b
R1 0.0605
a,c
wR2 0.1176
AC

3
max, min peaks, e/Å 0.277, – 0.227
_________________________________________________________________
a
I>2σ(I). b R1 = Σ | |Fo| – |Fc| | /Σ |Fo|. c wR2 = [Σ[w (Fo2 – Fc2)2] /Σ[w (Fo2)2]]1/2.
 ACCEPTED MANUSCRIPT

5. Supplementary material
5.1. Appendix A: Supplementary data

NMR spectra for new compounds and summary of crystallographic details for 1, 2b, 4, and 6a.

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Supplementary data related to this article can be found at:

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5.2. Appendix B: Supplementary data

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CCDC 1836199 – 1836202 contain the supplementary crystallographic data for compounds 1, 2b,

4, and 6a. These data can be obtained free of charge from The Cambridge Crystallographic Data

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Centre via www.ccdc.cam.ac.uk/data_request/cif.
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Author Information
M

Corresponding Author
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*
E-mail for M.R.M.: mmason5@utoledo.edu
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Notes

The authors declare no competing financial interests.

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Acknowledgments
C
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Acknowledgment is made to the National Science Foundation (CHE-0407542) and donors of the

Petroleum Research Fund, administered by the American Chemical Society (Grant 37172-AC3),

for partial support of this research. We thank Johanne LeCoq for initial work toward the synthesis

of compound 1. The CCD facility of the Ohio Crystallography Consortium located at the

University of Toledo was established with grants from the Ohio Board of Regents and ONR.
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Lithium to Calcium, John Wiley and Sons, Chichester, 2015, pp. 281-302.

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John Wiley, Chichester, 2016. https://doi.org/10.1002/9781119951438.eibc2333

SC
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U
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D

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C

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(b) J.-N. Pedeutour, K. Radhakrishnan, H. Cramail, A. Deffieux, Macromol. Rapid

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Polymerization Catalysts, John Wiley and Sons, Hoboken, 2010, pp. 1-28.

(c) E.Y.-X. Chen, T.J. Marks, Chem. Rev. 100 (2000) 1391.
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(d) A.R. Barron in: J. Scheirs, W. Kaminsky (Eds.), Metallocene-Based Polyolefins, vol.
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1, John Wiley and Sons, Chichester, 2000, pp. 33-67.

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(e) S. Pasynkiewicz, Polyhedron 9 (1990) 429.

[8] (a) M.P. Coles, R.F. Jordan, J. Am. Chem. Soc. 119 (1997) 8125.
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(b) M.P. Coles, D.C. Swenson, R.F. Jordan, V.G. Young Jr., Organometallics 16 (1997)

5183.
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[9] (a) P.A. Cameron, V.C. Gibson, C. Redshaw, J.A. Segal, M.D. Bruce, A.J.P. White, D.J.
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Williams, Chem. Commun. (1999) 1883.

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Highlights

• A new indole-based nitrogen-donor ligand has been synthesized

• The ligand adopts a bidentate or tridentate coordination mode when bound to a metal
• The ligand forms bimetallic complexes with two equivalents of aluminum trialkyl
• The bimetallic complexes undergo a dynamic exchange process in solution

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• A mechanism has been proposed for the dynamic exchange process

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