Coordination Chemistry Reviews 374 (2018) 387–415

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Coordination Chemistry Reviews

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Review

The chemistry of aluminum(I) with b-diketiminate ligands and

pentamethylcyclopentadienyl-substituents: Synthesis, reactivity and
applications
Yashuai Liu a, Jia Li a, Xiaoli Ma a,⇑, Zhi Yang a,b,⇑, Herbert W. Roesky c,⇑
a
School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, PR China
b
State Key Laboratory of Elemento-organic Chemistry, Nankai University, PR China
c
Institut für Anorganische Chemie der Universität Göttingen, Tammannstrasse 4, 37077 Göttingen, Germany

a r t i c l e i n f o a b s t r a c t

Article history: In the last two decades, tremendous progress has been made towards the development of compounds
Received 3 April 2018 with s- and p-block elements. b-Diketiminate ligands have been widely used in coordination chemistry
Accepted 2 July 2018 due to their versatile tunability in both electronic and steric properties. Aluminum complexes stabilized
by b-diketiminate ligands have been widely explored in stoichiometric studies to activate small
molecules. This review article highlights the recent progress of aluminum complexes supported by
Keywords: b-diketiminate ligands and Cp⁄(pentamethylcyclopentadienyl) substituents with univalent aluminum
b-Diketiminate
as reagents as well as aluminum hydrides in reactions.
Univalent aluminum
Aluminum hydride
Ó 2018 Published by Elsevier B.V.
Aluminacyclopropene
Reactivity
Pentamethylcyclopentadienyl

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
2. Univalent aluminum b-diketiminates: synthesis and reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
2.1. Synthesis of univalent aluminum with b-diketiminate ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
2.2. Reactions of MeNacNacAl(I) (5) with P4, S8, O2, and H2O. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
2.3. Reactions of MeNacNacAl(I) (5) with azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
2.4. Reactions of MeNacNacAl(I) (5) with other nitrogenous compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
2.5. Oxidative addition reactions of MeNacNacAl(I) (5) with molecules containing r-bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
2.6. Reactions of MeNacNacAl(I) (5) with further reagents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
3. Aluminacyclopropenes stabilized by b-diketiminate ligands: synthesis and reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
3.1. The synthesis of b-diketiminato aluminacyclopropenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
3.2. The reaction of compound 25 with ethyne, arylazide Ar*N3 and CO2, respectively . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
3.3. The reaction of compound 62 with further reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
3.3.1. The synthesis of five-membered aluminaheterocycles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
3.3.2. The synthesis of four-membered aluminaheterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
3.3.3. Collection of reactions with compound 62 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
4. Aluminum dihydrides employed b-diketiminate ligands in synthesis and reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
4.1. The synthesis of aluminum dihydrides stabilized by b-diketiminate ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
4.2. Reactions of NacNacAlH2 with various reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
4.2.1. Reactions of NacNacAlH2 with group 16 elements (S8, Se and Te) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
4.2.2. Reactions of NacNacAlH2 with boric acid, phosphoric acid and silicon glycol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
4.2.3. Reactions of NacNacAlH2 with compounds containing the –NH(NH2), and –OH(SH) functional groups . . . . . . . . . . . . . . . . . . . 403

⇑ Corresponding authors at: School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, PR China (Z. Yang).
E-mail addresses: maxiaoli@bit.edu.cn (X. Ma), zhiyang@bit.edu.cn (Z. Yang), hroesky@gwdg.de (H.W. Roesky).

https://doi.org/10.1016/j.ccr.2018.07.004
0010-8545/Ó 2018 Published by Elsevier B.V.
388 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

4.2.4. Reactions between NacNacAlH2 and unsaturated compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405

4.2.5. Reactions of NacNacAlH2 with further reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
4.2.6. Function as ligands for supporting transition metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
5. The synthesis, structure, and reactivity of pentamethylcyclopentadienyl and its derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
5.1. The synthesis of (Cp*Al)4 and its derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
5.2. The reactivity studies of (Cp*Al)4 and its derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
5.3. Function as ligand in coordination chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
5.3.1. Main-group metal complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
5.3.2. Transition metal complexes with Cp*Al as ligand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
6. Summary and conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414
Acknowledgement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414

1. Introduction membered AlC2–ring, due to its highly strained structure and high
reactivity. Apart from aluminum hydrides and aluminacyclo-
b-Diketiminate ligands are also known as ‘‘[NacNac]
” sub- propene, the stoichiometric transformation of NacNacAl(I) has also
stituents. They have emerged to one of the important ligands in been explored widely owing to its lone pair of electrons and a for-
coordination chemistry for main group [1–3] and transition metals mally vacant p-orbital affording the high electrophilic and nucle-
[4–14]. The ligands are tunable and versatile through the modifica- ophilic reactivity.
tion of the ligand backbone and the substituents at the nitrogen In recent years several reviews have been published focusing on
atoms. According to this particular property, b-diketiminate various aluminum complexes [1,2,21,23–31]. In contrast to these
ligands have been widely used to assemble a variety of complexes reviews, we report herein on the synthesis of aluminum
with metals in a broad range of oxidation states. b-diketiminato complexes and their applications in various trans-
A number of transition metal complexes were synthesized with formations as well as on the chemistry of (Cp*Al)4.
high reactivity to activate small molecules or used as catalysts in
organic reactions [15–19]. In recent years s- and p-block elements
were brought into focus containing active functional groups and 2. Univalent aluminum b-diketiminates: synthesis and
achieved great progress. Aluminum is the most abundant metal reactivity
in the earths’ crust with the advantage of low toxicity and ubiqui-
tous availability. This inspired chemists to explore various types of Aluminum prefers to be in the energetically +3 oxidation state
aluminum compounds with high thermodynamic stability as well due to its relative stability compared with lower oxidation states.
as high reactivity to study their properties and applications in The low oxidation states of aluminum have been reported
catalysis and new materials. [32,33], and aluminum(I) compounds are analogous to carbenes
Aluminum complexes with b-diketiminate ligands have with distinct reactivity, which has received considerable interest
emerged as research hotspots in literature [20–22]. Numerous in the last 17 years. The stoichiometric reactions of aluminum(I)
investigations focused on stoichiometric transformations of supported by b-diketiminate with a number of reagents will be
b-diketiminato complexes with four-coordinate aluminum. The reported herein.
most interesting studied functional group on the aluminum atom
was the hydride and the three-membered AlC2-ring system. Alu- 2.1. Synthesis of univalent aluminum with b-diketiminate ligands
minum hydrides containing negative polarized hydrogen could
be used for reactions with various organic or inorganic molecules b-Diketiminato aluminum alkyls and aluminum halides are
as reducing agents. Furthermore, aluminum hydrides with well- basic organometallic intermediates for further synthesis of
modified substituents at the aluminum center could catalyze organoaluminum complexes. According to the previous works,
Me
organic reactions, such as dehydrocoupling, hydroboration, and NacNacAlI2 (1), MeNacNacAlMe2 (2), t-BuNacNacAlI2 (3),
hydrosilylation. Various aluminum containing heterocycles were t-Bu
NacNacAlMe2 (4) (L = NacNac = [ArNC(R)CHC(R)NAr]
and
successfully synthesized through the reactions of the three- Ar = 2,6-iPr2C6H3, R = Me or t-Bu) are synthesized by one or two

Scheme 1. Synthesis of NacNacAl(I).

 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415
Scheme 2. Reactions of NacNacAl(I) with small molecules.
steps from the initial b-diketiminate ligands L1 (ArNHC(Me)CHC
(Me)NAr) and L2 (ArNHC(t-Bu)CHC(t-Bu)NAr) [34–36]. The first
synthesis of aluminum(I) b-diketiminato complex MeNacNacAl(I)
(5) was pioneered by Roesky and coworkers following the syn-
thetic route shown in Scheme 1, Eq. (1) [37]. The MeNacNacAl(I)
(5) was prepared through reduction of the corresponding
Me
NacNacAlI2 (1) with potassium. In the same way Cui et al. syn-
thesized an analogous t-BuNacNacAl(I) (6) with tertiary butyl
groups instead of methyl substituents [36]. The synthetic route is
shown in Scheme 1, Eq. (2).
Me
2.2. Reactions of NacNacAl(I) (5) with P4, S8, O2, and H2O
The aluminum(I) complex 5 can activate elemental P4, O2, and
S8, respectively (Scheme 2). The partial reduction of white
phosphorus with 2 equiv. of 5 at room temperature resulted in
the formation of the first main group complex of composition
Fig. 1. The X-ray single crystal structure of the [(L1Al)2(l-P4)] (7).
389
[(L1Al)2(l-P4)] (7) in good yield with the {P4}4
anion [38]. Com-
pound 8 was prepared in a good yield by the reaction of 5 with ele-
mental sulfur in a molar ratio of 2:6. However, when 5 was treated
with sulfur in a ratio of 2:3, product 8 was also formed, although
the yield decreased to 10%. Two (l-S3) chains in 8 connect two alu-
minum atoms to form an Al2S6 crown-like ring [39]. O2 inserts into
the Al-alkyl bonds of alkylaluminum(III) compounds leading to
aluminum alkoxides [40–42] or alkylperoxides [43]. MeNacNacAl
(I) (5) could be oxidized using oxygen directly to yield the oxide-
bridged [(L1Al)2(l-O)2] (9), which further reacted with water to
give an aluminum oxide hydroxide 10 [44]. Aluminum hydroxides
are important intermediates for the synthesis of oxo-bridged
hetero-bimetallic compounds [45,46]. Finally 6 was reacted with
1 equiv. of water to afford directly aluminum hydroxide 11 in high
yield [36]. The X-ray single crystal structures of 7 and 8 are shown
in Figs. 1 and 2.
Me
2.3. Reactions of NacNacAl(I) (5) with azides
It is well known that most organic azides are not kinetically
stable and easily react with elimination of N2. Due to this high
Fig. 2. The X-ray single crystal structure of 8 with an Al2S6 core.
390 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

Scheme 3. The reaction of 5 with azides.

reactivity, a number of different azides were explored in reactions

Fig. 3. The X-ray single crystal structure of the aluminatetrazole 14.
with NacNacAl(I) to yield interesting aluminum-nitrogen
compounds.
Roesky, Power, and coworkers investigated the reaction of alu-
minum (I) b-diketiminate complex (5) with the sterically encum-
bered azide N3-2,6-Trip2C6H3 (Trip = 2,4,6-iPr3C6H2), yielding
[{HC(MeCDippN)2}AlN-2,6-Trip2C6H3] (12), which was the first
stable monomeric imide of the heavier Group 13 elements
[47,48]. Furthermore N3SiMe3, N3SiPh3, and N3C10H15, respectively,
were reacted with compound 5 resulting in aluminatetrazoles
[R = SiMe3 (13), SiPh3 (14), C10H15 (15)] [49,50] (Scheme 3). The
formation of aluminatetrazoles suggested that those groups which
are not bulky enough to stabilize the expected monomeric LAlNR
with an Al@N double bond. The intermediates with the Al@N
double bond react further under [2+3] cycloaddition with
additional molecules of azide to yield compounds 12–15. The
molecular structure of 14 is shown in Fig. 3. Furthermore, the reac-
tion of 5 with t-BuSi(N3)3 was explored and resulted in compound
16 (Fig. 4) [50]. The supposed Al@N intermediate A was formed by
N2 elimination and further rearrangement under migration of one
N3 group from the Si to the Al atom forming the N = Si species B.
Finally 16 was obtained by [2+2]-cycloaddition of two molecules
of B. The proposed formation of 16 is shown in Scheme 4.
In addition to the experiments mentioned above, a number of
reactions were performed to prepare analogous group 13 imides.
The reaction of 5 with bulky N3-2,6-Ar2C6H3 (Ar = 2,6-iPr2C6H3)

Fig. 4. Molecular structure of compound 16 with a four-membered N2Si2 ring.

 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415 391

Scheme 4. The reaction of 5 with t-BuSi(N3)3.

Scheme 5. The reaction of 5 with 2,6-Ar2C6H3N3 (Ar = 2,6-iPr2C6H3).

Fig. 5. X-ray single crystal structure of compound 20 with an AlANH bond.

Fig. 6. X-ray single crystal structure of the CAH activated aluminum hydroxide 21.

afforded two isomers 17 and 18 [51] (Scheme 5). The proposed

mechanism of the reaction shows two different types of
intramolecular addition reactions. Furthermore 18 could be con-
verted to 17 by thermal treatment. Cui et al. synthesized a similar
structure of composition 19, which can be compared with that of
17 [36]. Moreover, the reaction of 5 with N3-2,6-Mes2C6H3 contain-
ing a small amount of water resulted in the respective isolation of
20 (Fig. 5) and 21 (Fig. 6) [44]. The AlAN bond imposed by the
bulky Ar0 (Ar0 = 2,6-Mes2C6H3N3, Mes = 2,4,6-iPr3C6H2) in 20 might
preferentially react with H2O to yield 21 and an aromatic amine
[44] (Scheme 6).
392 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

Scheme 6. The reaction of 5 with 2,6-Mes2C6H3N3.

2.4. Reactions of MeNacNacAl(I) (5) with other nitrogenous compounds

Reactions of 5 with further reagents were studied. In many

organic and organometallic reactions, diphenyldiazomethane can
work as an effective precursor to generate the transient :CR2 under
elimination of N2 [52,53]. Therefore, it could work as electron-rich
species for the reaction with aluminum(I). To explore this reaction,
aluminum(I) compound 5 was treated with 2 equiv. of diphenyl-
diazomethane to yield the first example of an unexpected
diiminylaluminum compound L1Al(N@CPh2)2 22 [54]. The authors
assumed that 22 was obtained via the initial generation of
Ph2C@NN@CPh2 followed by its oxidative addition to 5 (Scheme 7).
Treatment of 5 with 2 equiv. of steric isocyanides was investi-
gated by Cui et al. [36]. Reactions of silylenes with bulky
isocyanides were successfully conducted and reported before
[55–61]. The addition of two equiv. of CNAr in toluene to a dilute
solution of 6 at room temperature afforded compound 23. How-
ever, when the dilute solution of 6 was replaced by the suspension
of 6 in a small amount of toluene, compound 24 could be obtained
with three heterocyclic rings (Scheme 8). The molecular structures
of 23 and 24 are shown in Figs. 7 and 8. Fig. 7. X-ray single crystal structure of compound 23.
Aluminum(I) compound 5 undergoes [1+2]-cycloaddition with
substituted or unsubstituted alkynes to give aluminacyclopropene
derivatives, and these [1+2]-cycloaddition reactions were well
studied by Roesky et al. [62,63] (Scheme 9). NacNacAl(I) reacted
with ethyne in the temperature range from
78 °C to room tem-
perature and successfully gave the first stable aluminacyclo-
propene LAl(g2-C2H2) [62]. Since the discovery of LAl(g2-C2H2),
the scope of alkynes including mono- and disubstituted alkynes
and diyne were investigated and afforded the corresponding com-
pounds 25–28. DFT calculations showed that an interaction
between the Al(I) center and the C„C unit needs almost no
activation energy [63]. Inspired by these cycloaddition reactions,

Scheme 7. The reaction of 5 with diphenyldiazomethane.

Fig. 8. X-ray single crystal structure of compound 24.

Scheme 8. The reaction of 6 with isocyanide.

 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415 393

Scheme 9. The [1+2]-cycloaddition reactions of 5 with alkynes.

Scheme 10. The reaction of 5 with azobenzene.

azobenzene reacted with 5 via a [1+2]-cycloaddition to afford the

unexpected compound of 29 [64] (Scheme 10). It is assumed that
5 reacted with azobenzene via [1+2]-cycloaddition to give inter-
mediate C, which was not stable and rearranged to compound 29
Scheme 11. Reactions of 5 with HX (X = H, SiHR2, BPin etc.).
by cleavage of the NAN bond and migration of an ortho hydrogen
atom from one of the N-Ph rings. Furthermore, the structure of the
complex 29 was confirmed by single crystal X-ray structural anal- Me
NacNacAl(I) proceeds concertedly and therefore, involving simul-
ysis (Fig. 9).
taneous HAX bond breaking and AlAH and AlAX bond making.
Consequently a number of oxidative addition reactions of HAX with
Me the aluminum(I) center emerged. Nikonov et al. reacted 5 with
2.5. Oxidative addition reactions of NacNacAl(I) (5) with molecules
disulfides, alkyl sulfides, and diphosphides to obtain the corre-
containing r-bonds
sponding complexes MeNacNacAl(SPh)2 (30), MeNacNacAlEt(SEt)
(31), and MeNacNacAl(PPh2)2 (32), respectively [67] (Scheme 11,
In this chapter, oxidative reactions under cleavage of r-bonds in
Eq.6).
molecules will be reported. Nikonov and coworkers [65]
Apart from the oxidative addition of H-X to NacNacAl(I),
(Scheme 11, Eq. (5)) reacted compound NacNacAl(I) (5) with HX
another type of oxidative addition of NacNacAl(I) was explored.
(X = H, H, Si, B, Al, C, N, P, O) and prepared a series of hydride deriva-
Schulz and coworkers reacted MeNacNacAl(I) with Et2E-EEt2
tives with four-coordinate aluminum NacNacAlH(X). Note, these
(E = Sb, Bi) with the insertion into the weak EAE bond leading to
reactions are reversible, proving the possibility of reductive elimi-
the formation of NacNacAl(EEt2)2 (33 and 34) [68] (Scheme 12).
nation of MeNacNacAlH(X). To a better understanding of the oxida-
The oxidation of small molecules (H-X, RE-ER) to NacNacAl(I)
tive addition of H-X to the aluminum(I) compound, computational
has been widely explored in recent years. The formation of com-
investigations have been explored within the density functional
pounds with a CAAl bond by using 5 as a precursor was studied
theory framework [66]. According to the computational study, the
with the result that either CAF or CAO bonds are formed. The
reactions of alkyl compounds containing RAF or RAOR bonds with
aluminum dihydride 35 catalyzed by transition metals have been
explored [69,70]. As shown in Scheme 13, the possible mechanism

Scheme 12. Reaction of 5 with E2Et4 (E = Sb, Bi).

Scheme 13. Reactions of R-X (X = F, OR) with aluminum dihydride (35) catalyzed
Fig. 9. X-ray single crystal structure of complex 29. by transition metals.
394 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

was supposed that the intermediate MeNacNacAl(I) (5) was formed
from 35 catalyzed by transition metal and then reacted with RAX
(X = F or OR) with the cleavage of the RAX bond under formation of
Me
NacNacAlR(X). Inspired by this assumption, a facile oxidative
addition of fluoroarenes, fluoroalkanes and benzofuran, respec-
tively, to MeNacNacAl(I) in high yields was reported by Crimmin
[71] (Scheme 14, Eq. (7)). To prove the mechanism, (Scheme 14)
complex 5 was treated with fluoroarenes and fluoroalkanes and
the reactions proceeded rapidly in high yields. The activation of
the sp2 CAF bond of fluoroarene (36) and even the sp3 CAF bond
of fluoroalkanes to synthesize MeNacNacAlF (R or ArF) (37–40)
was possible. The oxidative addition of benzofuran with 5 could
proceed successfully by optimizing the reaction conditions:
improving the temperature to 80 °C and lingering the time to 24
h. The similar oxidative addition of 5 with compounds containing
CAF or CAO bonds have also been accomplished by Nikonov

Me
Scheme 14. The oxidative addition of compounds with CAF and CAO bonds, respectively to NacNacAl(I) (5).

Scheme 15. The proposed mechanisms of CAF added to the Al(I).

Scheme 16. Facile C@S and P@S bond cleavage by NacNacAl(I) (5).
 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415
Scheme 17. Cleavage of C@N, C@O and P@O bonds, respectively and additions to
Fig. 10. X-ray single crystal structure of compound 45.
et al. [72], shown in Scheme 14, Eq. (8). Note, compound 5 could
cleave the CAF bonds of polyfluorinated benzene, as well as
tetra- and trifluorinated substrates, respectively. These precursors
have high fluorine content and the addition of aryl CAF bonds to 5
depends on the degree of fluorination on the aromatic substrate.
Some studies of the mechanisms of the addition of compounds
with CAF and CAO bonds, respectively, to NacNacAl(I) have been
investigated [72,73], and the reactions include the cleavage of aryl
CAF bonds and oxidative addition to the aluminum center of com-
pound 5. Kinetic studies by Nikonov et al. showed that the overall
reaction is of second-order, which is consistent with a simple one-
step CAF oxidative addition process [72]. The investigation of the
oxidative addition of CAF bonds to NacNacAl(I) by DFT calculations
was accomplished by Pitsch and Wang [73]. They demonstrated
that the mechanism of the activation of CAF bonds by oxidative
addition to NacNacAl(I) is different between C(sp2)-F and C(sp3)-
F. Two mechanisms were studied, (i) the C(sp2)-F was added to
the Al(I) center by a concerted mechanism to synthesize the corre-
sponding product; (ii) the C(sp3)-F is added via a stepwise mecha-
nism involving a rate-determining fluoride transfer and facile
395
Me
NacNacAl(I).
Fig. 11. X-ray single crystal structure of compound 46.
cation–anion combination. The proposed mechanisms are illus-
trated in Scheme 15.
Besides the oxidative addition reactions of NacNacAl(I) men-
tioned above, the cleavage of unsaturated bonds (C@S, P@S, C@N,
C@O, P@O) and their addition products to NacNacAl(I) have been
reported. Treatment of NacNacAl(I) with thioureas resulted in the
oxidative cleavage of the C@S bond and gave the corresponding
compounds 42 and 43, which were the first monomeric aluminum
complexes with an Al@S double bond stabilized by N-heterocyclic
carbene [74] (Scheme 16, Eq. (9)). In a similar fashion, NacNacAl(I)
reacted with triphenylphosphine sulfide via the oxidative cleavage
of the P@S bond and the formation of 44 [74] (Scheme 16, Eq. (10)).
The existence of the Al@S bond in 43 was supported by DFT
calculations.
Me
NacNacAl(I) (5) reacted with cyclic guanidine TolN = SIMe to
afford the carbene-ligated Al(III) amide complex 45 via the
unprecedented cleavage of the C@N bond of TolN = SIMe [75].
The reaction proceeded via addition of TolN = SIMe to the Al(I) cen-
ter affording intermediate 45A and following with rearrangement
to give Al(III) amido-carbene complex 45 (Scheme 17). In a DFT
396 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

study, intermediate 45A was assumed, which reacted further with
a second molecule of 5 via multistep proton rearrangement to
afford a more stable amido-carbene isomer 45 and molecule 5.
To investigate the oxidative cleavage of unsaturated bonds of
C@O and P@O units, the reactions of NacNacAl(I) with urea and
phosphine oxides, respectively were accomplished and gave the
unexpected aluminum complexes 46–48 [76]. They were synthe-
sized differently from the complexes (42–45) mentioned earlier,
as shown in Scheme 17. The DFT study supported that these reac-
tions proceed via a bimolecular mechanism in which either the
basic aluminum(I) center or the transient Al@O species deproto-
nate one methyl group of the NacNac ligand. The crystal structures
of 45 and 46 are shown in Figs. 10 and 11.
2.6. Reactions of Me
NacNacAl(I) (5) with further reagents
The reaction of MeNacNacAl(I) with PhB(OH)2 in a 1:2 M ratio
resulted in the formation of MeNacNacAl[(OBPh)2O] (49). The reac-
tion may proceed in two steps: (i) NacNacAl(I) reacted with two
equiv. of PhB(OH)2 to form the intermediate 49A; (ii) the central
Al(I) was oxidized to NacNacAl(OBPhOH)2 with elimination of
one equiv. each of H2 and H2O to form 49 (Fig. 12) [77]
(Scheme 18).

Fig. 12. X-ray single crystal structure of compound 49.

Fig. 13. X-ray single crystal structure of compound 52.

Scheme 18. The reaction of NacNacAl(I) with PhB(OH)2.

Scheme 19. Reactions of NacNacAl(I) with further reagents.

 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415
Fig. 14. X-ray single crystal structure of compound 55.
Fig. 15. X-ray single crystal structure of compound 56.
Scheme 20. Reaction of NacNacAl(I) with 1,3-diisopropyl-4,5-dimethyl-2-ylidene.
397
The solid-state reaction of NacNacAl(I) with imidazol-2-ylidene
at 120 °C was explored to give the aluminum monohydride N-
heterocyclic carbene adducts [{HC[C(CH2)NAr](CMeNAr)}AlH-{CN
(R)C2Me2N(R)}] 50 and 51, respectively [54]. Obviously, a hydride
of a methyl group migrates from ligand ‘‘NacNac” to the aluminum.
So far the exact mechanism is not known (Scheme 19). NacNacAl(I)
reacted with cAAC: ? AlX3 (X = Cl, I) (cAAC = cyclic alkyl amino
carbene) leading to the asymmetric Al(II)–Al(II) compounds 52
and 53, in which two aluminum atoms bear different ligand envi-
ronments and different numbers of coordinated halogen atoms
[78]. Furthermore, theoretical calculations were carried out to sup-
port the bonding situation of the structures of 52 and 53. According
to the theoretical calculations, NacNacAl(I) has both Lewis acid and
Lewis base properties at the same aluminum center and the exper-
imental evidence was demonstrated due to its reactivity with B
(C6F5)3 by Yang et al. [79]. MeNacNacAl(I) reacted with B(C6F5)3 in
a 1:1 ratio affording the stable four coordinated aluminum(I) com-
pound 54 (Scheme 19). Kinjo and coworkers unexpectedly found
that the Al(I) center of MeNacNacAl(I) inserted into the CAO bond
of L2PhB (L = oxazol-2-ylidene) resulting in a unique organoboron
species 55 involving either an Al, N, O mixed heterocyclic carbene
or an anionic (amino)(boryl)carbene fragment [80] (Scheme 19).
Moreover DFT calculations were employed to determine their elec-
tronic properties. The molecular structures of 52 and 55 are shown
in Figs. 13 and 14.
t-Bu
NacNacAl(I) (6) was used instead of MeNacNacAl(I) (5) and
reacted with 1,3-diisopropyl-4,5-dimethyl-2-ylidene (R = iPr)
in THF at 0 °C leading to the formation of product 56 (Fig. 15).
During the reaction the six-membered ring is converted to a
Scheme 21. Synthesis of 60 and 61.
Scheme 22. The synthesis of aluminacyclopropenes.
398 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

Scheme 23. The synthesis of complex 28 via two different reaction routes.

Scheme 24. Reactions of 25 with C2H2 and Ar*N3.

five-membered ring. The structure of 56 is extremely air and mois-

ture sensitive and reacted with EH (E = PhCC, PhNH) and CO, respec-
tively to yield the aluminum complexes 57–59 [81] (Scheme 20).
Additionally, diisocyanate aluminum(III) complex MeNacNacAl
(NCO)2 (60) and diisothiocyanate aluminum(III) complex MeNacNa-
cAl(NCS)2 (61) were obtained via the reaction of compound 5 with
AgX (X = NCO and NCS) (Scheme 21). Compounds 60 and 61 are the
first examples where two pseudohalide substituents are bound to
aluminum(III) [82].
In conclusion, NacNacAl(I) exhibits high reactivity with a num-
ber of reagents with the consequence that in the future many
interesting aluminum compounds will be generated using Al(I)
compound as a precursor.
3. Aluminacyclopropenes stabilized by b-diketiminate ligands:
synthesis and reactivity
3.1. The synthesis of b-diketiminato aluminacyclopropenes
Heavier main group cyclopropene analogues attract chemist’s
attention due to their highly strained structure and high reactivity.
Fig. 16. The X-ray single crystal structure of the five-membered aluminaheterocy-
cle 69.
To the best of our knowledge, many studies on such species have
been contributed to group 14 compounds (Si, Ge, Sn). The group
13 cyclopropene analogues are mainly centered on boron [83,84],
and stable neutral metallacyclopropenes of aluminum have been
first reported in 2001 by Cui et al. [48] (Scheme 22). Compound
3 was synthesized via the reaction of L1AlMe2 (1) with 2 equiv. of
I2 in toluene [34]. LAl(I) is a carbene-like species but did not react
with bis-(trimethysilyl)alkine, diphenylalkine, and 1-phenyl-2-
trimethylsilylalkine, respectively in a [1+2]-cycloaddition reaction.
The reductive coupling reaction of 3 in situ in the presence of alki-
nes successfully resulted in the formation of aluminacycloprope-
nes 62–64 in modest yields.
Another method of aluminacyclopropenes was presented by
Zhu et al. [63]. Compound 28 could be synthesized not only from
compound 3 via reduction by potassium in the presence of

Scheme 25. Synthesis of five-membered heterocyclic aluminum compounds from the precursor 62.
 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415
Fig. 17. The X-ray single crystal structure of 71.
Scheme 26. The conversion of 62 with CS2 to 71.
Scheme 27. The synthesis of compounds 72 and 74.
399
Me3SiC„CC„CSiMe3, but also from the reaction of compound 62
with Me3SiC„CC„CSiMe3 (Scheme 23).
3.2. The reaction of compound 25 with ethyne, arylazide Ar*N3 and
CO2, respectively
Aluminacyclopropene 25 was synthesized via the reaction of
Me
NacNacAl(I) (5) with ethyne in the ratio of 1:1. The 1:2 reaction
of L1Al(I) with ethyne resulted in the formation of compound 65
containing an ethylene and a CCH group attached to the aluminum
center in the temperature range of
78 °C to 20 °C [62]. This result
proved that compound 25 could further react with ethyne to yield
compound 65. In addition, the reaction of 25 with a bulky azide
Ar*N3 was carried out to give a four-membered heterocycle 66
(Scheme 24). Accordingly, the end-on Ar*N3 insertion into the AlAC
bond unambiguously reveals the initial interaction between an Al
center and the terminal N atom of the azide group.
3.3. The reaction of compound 62 with further reagents
3.3.1. The synthesis of five-membered aluminaheterocycles
The strain within the AlC2-three-membered ring increases the
reactivity of the AlAC bonds toward unsaturated molecules, leading
preferentially to five-membered aluminum containing ring systems
of compounds 67–70 [48] (Scheme 25). Reaction of 62 with CO2
proceeded smoothly at room temperature to yield the heterocyclic
aluminum compound 67 in high yield. The reaction of 62 with
Fig. 18. The X-ray single crystal structure of compound 72.
400 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415
Scheme 28. Reactions of 62 with CO and t-BuNC, respectively.
benzophenone (Ph2CO) in diethyl ether at room temperature
resulted in the aluminadihydrofuran 68. Treatment of 62 with ben-
zonitrile PhCN yielded the five-membered heterocyclic aluminum
compound 69. t-BuCN reacted with 62 to generate the first alu-
minum bis(iminato) complex LAl[N2(Ct-Bu)2] (70). The X-ray single
crystal structure of 69 with a five-membered aluminaheterocycle is
shown in Fig. 16.
A seven-membered aluminum sulfur allenyl heterocycle 71
(Fig. 17) was obtained via the reaction of 62 with CS2 [85]
(Scheme 26). The mechanism for the formation of 71 was dis-
cussed. Compound 62 reacted with CS2 affording the intermediate
71A, which resembles the reaction of 62 with CO2. The intermedi-
ate 71A reacted further with another molecule of 62 to give inter-
mediate 71B. Finally, the latter one was converted into compound
71 with elimination of one molecule of Me3SiCCSiMe3.
Moreover, compound 62 reacted with pyridine to afford the
(1,2-dihydropyridyl) aluminum species L1Al[C2(SiMe3)2CHN–
(C4H4)] (72) with an AlC3N five-membered ring [86] (Scheme 27).
The minor side product 73 was also recovered. The reaction exhib-
Fig. 19. The X-ray single crystal structure of 75.
ited a high selectivity to undergo a pyridine 1,2-insertion reaction
with the final formation of the stable AlC3N five-membered ring of
72 (Fig. 18). In contrast, the hydrolysis of 62 at low temperature
resulted in the ring cleavage of 62 to afford an acyclic aluminum
alkenyl hydroxide LAl(OH)[C(SiMe3)CH(SiMe3)] (74).
3.3.2. The synthesis of four-membered aluminaheterocycles
In addition to the five-membered aluminum heterocycles, four-
membered aluminum heterocycles could be synthesized via the
reaction of aluminacyclopropene 62 with unsaturated compounds.
The insertion of CO and isocyanide into an AlAC bond of the AlC2
ring of 62 was carried out by Cui et al. [87] (Scheme 28). Com-
pound 62 was treated with two equiv. of t-BuCN to form the
five-membered aluminum compound 70 [48], while the reaction
proceeds rapidly to give the AlC3 aluminacyclobutene 75, when
the ratio of 62 with t-BuCN is 1:1 [87]. The red solution of 62
was exposed at room temperature to purified CO atmosphere to
afford the corresponding product 76. Interestingly, one oxygen
atom of dioxygen could selectively insert into the AlAC(O) bond
Fig. 20. The X-ray single crystal structure of the cyclopropenylaluminum derivative
77.
 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415
of 76 to result in the formation of compound 67, which was
obtained via the reaction of 62 with CO2 mentioned before. Alco-
holysis of aluminacyclobutenone 76 resulted in the formation of
the cyclopropenylaluminum derivative 77 under formation of alu-
minum hydroxides LAlOH(OR) (R = H, Et, t-Bu) (78–80) [88]. The
existence of the two different functional groups in the strained
AlC3 ring of 76 may be responsible for the high reactivity. The latter
definately reacts with oxygen to yield the stable five-membered
cycloaluminum compound 67. The X-ray single crystal structures
of 75 and 77 are shown in Figs. 19 and 20.
3.3.3. Collection of reactions with compound 62
The solution of 62 in diethylether at
78 °C exposed to dry
dioxygen afforded the corresponding aluminum monohydroxide
81 with elimination of C2(SiMe3)2 [89]. The CAH bond of one
CHMe2 group on the Dipp(2,6-iPr2C6H3) ring was activated by
dioxygen (Scheme 29). It was assumed that the reaction proceeds
in the following steps: (i) compound 62 reacts with dioxygen form-
ing an aluminum peroxide intermediate 81A; (ii) 81A is converted
Scheme 29. The synthesis of CAH bond activated aluminum hydroxide and its
proposed mechanism.
Fig. 21. The X-ray single crystal structure of 81.
401
into intermediate 81B via OAO bond cleavage accompanied by the
intramolecular oxidation of a CAH bond of one CHMe2 group on
the Dipp ring; (iii) product 81 with a stable six-membered
AlNCCCO ring is formed via dimerization with intramolecular
proton-transfer and elimination of bis(trimethylsilyl)acetylene.
The molecular structure of 81 is shown in Fig. 21.
Apart from the reactions inducing some new species with
higher coordinate aluminum mentioned above, compound 62
was reacted with RN3 (R = 2,6-Trip2C6H3, SiPh3) to give the corre-
sponding products 12 and 82 in high yields [48] (Scheme 30).
In conclusion aluminacyclopropenes are mainly synthesized
from the reaction of NacNacAlI2 and NacNacAl(I) with alkynes.
They are thermodynamic stable and exhibit high reactivity with
various kinds of reagents. The reactivity of aluminacyclopropenes
was explored in the past decades and has achieved great progress.
Further studies are necessary to cover the potential of these
reagents.
4. Aluminum dihydrides employed b-diketiminate ligands in
synthesis and reactivity
The hydrogen atoms of aluminum hydrides are negatively polar-
ized and exhibit strong reducing properties. Moreover, they have
important applications in coordination chemistry, biochemistry,
pharmaceutical and material chemistry as well as in catalysis. Alu-
minum hydrides can react with a variety of compounds, such as
small molecules, unsaturated species, amines, and ionic compounds
to generate novel organo aluminum compounds. The application of
aluminum hydrides in catalysis was recently published [21].
4.1. The synthesis of aluminum dihydrides stabilized by b-diketiminate
ligands
Recently b-diketiminato aluminum dihydrides (NacNacAlH2)
have been investigated. Traditionally they are prepared via two dif-
ferent synthetic routes, taking the synthesis of L1AlH2 (35) as exam-
ple [90]. L1AlH2 (35) could be obtained via the addition of the
solution of AlH3NMe3 to the solution of L1 in toluene at room tem-
perature. Moreover, the reaction of L1 and a little excess of LiAlH4 in
toluene resulted in the formation of L1AlH2 (35) (Scheme 31).
4.2. Reactions of NacNacAlH2 with various reagents
4.2.1. Reactions of NacNacAlH2 with group 16 elements (S8, Se and Te)
In 2004 Jancik et al. [91] reported on the reaction of L1AlH2 (35)
with elemental Se and Te, respectively, in the presence of catalytic
Scheme 30. The reaction of 62 with 2,6-Trip2C6H3N3.
Scheme 31. Synthesis of aluminum dihydride L1AlH2.
402 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415
Scheme 32. Reactions of L1AlH2 (35) with elemental S, Se, Te.
Scheme 33. Possible mechanism for the formation of [L1Al(l-Y)2AlL1] (Y = Se, Te).
Fig. 22. The X-ray single crystal structure of 86.
Scheme 34. Reactions of L1AlH2 with Se and S8.
amounts of phosphanes as catalyst resulting in the formation of
[L1Al(m-Se)2AlL1] (83) and [L1Al(m-Te)2AlL1] (84) (Scheme 32).
While [L1Al(m-S)2AlL1] (86) could not be obtained directly via the
reaction of L1AlH2 (35) with sulfur. The intermediate L1Al(SH)2
(85) was synthesized directly instead, after reacted with another
molecule of L1AlH2 leading to [L1Al(l-S)2AlL1] (86). A possible
mechanism for the formation of [L1Al(l-Y)2AlL1] (Y = Se, Te) was
proposed (Scheme 33). The X-ray single crystal structure of 86 is
shown in Fig. 22.
Moreover Cui et al. synthesized [L1(HSe)AlSeAl(SeH)L1] via the
reaction of L1AlH2 with Se powder at room temperature and subse-
quent heating at 60 °C resulted in the formation of [L1Al(SeH)SeAl
(SeH)L1] (88) with elimination of H2Se [90] (Scheme 34, Eq. (11)).
Comparable structures of [L1Al(SH)SAl(SH)L1] (89) and [L1Al(SH)
OAl(SH)L1] (90) were obtained successively from the reaction of
L1AlH2 with S8. Furthermore, hydrolysis of L1AlH2 with different
equivalents of H2O gave different products, one of them could be
transformed into compound 89 (Scheme 35) [92].
4.2.2. Reactions of NacNacAlH2 with boric acid, phosphoric acid and
silicon glycol
In 2006, Yang et al. reacted aluminum dihydride L1AlH2 with
PhB(OH)2 in a 1:2 M ratio resulting in the formation of L1Al
[(OBPh)2O] (49) with elimination of two molecules of hydrogen
and a molecule of H2O. Compound 49 has a six-membered planar
AlO3B2 ring [77]. A two-step mechanism was proposed
(Scheme 36). The mechanism for the product formation: (i)
L1AlH2 reacted with two molecules of PhB(OH)2 with elimination
of H2 leading to the intermediate L1Al[OB(OH)Ph]2; (ii) intramolec-
ular dehydration condensation of L1Al[OB(OH)Ph]2 resulted in the
desired product 49. Furthermore, various analogous compounds
92–97 were synthesized, via reacting L1AlH2 with RB(OH)2 under
elimination of H2 and H2O [93–95] (Scheme 37). Moreover
 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415 403

Scheme 35. Hydrolysis of L1AlH2 with different amounts of H2O and treatment with sulfur.

Scheme 36. The reaction of L1AlH2 with PhB(OH)2 resulting in L1Al[(OBPh)2O] (49).

Scheme 38. The reaction of L1AlH2 with 2,6-dimethoxyphenylboronic acid.

compound (L1AlO)2B(2,6-OCH3C6H4)(l-O) (98) containing the
Al2BO3 six-membered ring was accomplished via the reaction of
L1AlH2 with 2,6-dimethoxyphenylboronic acid [96] (Scheme 38).
The reaction proceeded in two steps: L1AlH2 reacted with boronic
acid with the elimination of H2 and the hydrolysis of the interme-
diate 98A resulted in product 98.
In general the reaction of LAlH2 with boronic acid to synthesize
aluminum compounds with the core structure of Al–O–B are less
developed, when compared with other aluminum nonmetallic oxi-
des of composition Al–O–X (X = Si, P, C). The latter have been well
studied. Aluminum compounds containing the Al–O–X (X = Si, P, C)
moiety are important in catalysis and material science. Yang et al.
synthesized a series of compounds with the Al–O–X (X = Si, P, C)
structural moiety via the reactions of L1AlH2 with diphenylsilane-
diol, phosphonic acids, and pyrocatechol, respectively [97]
(Scheme 39). Compound 99 contains the Al-O-Si-O-Al
heterotrimetallic dioxide chain and compound 101 displays a
P–O–Al–O–P chain structure, while complex 100 features an
Al(l-O)2P four-membered ring and 102 exhibits a benzo-
aluminum-dioxide with a five-membered ring.
4.2.3. Reactions of NacNacAlH2 with compounds containing the –NH
(NH2), and –OH(SH) functional groups
Amino acids, a significant class of organic compounds, exhibit-
ing the potential donor sites COOH and NH2 show high ability to
stabilize metal ions. They are widely applied in coordination chem-
istry [98]. Compounds with the functional groups –NH(NH2), –OH
(SH), and –COOH could react with active organometallic com-
pounds to afford a series of novel derivatives, which feature
organic–inorganic hybrids containing AlAN, AlAO and AlAS bonds,
respectively. The aluminum dihydride is a preferred precursor due
to its high ability to react with compounds exhibiting the func-
tional –NH(NH2), –OH(SH), and –COOH group, respectively, under
hydrogen elimination.

Scheme 37. Compounds obtained from the reaction of L1AlH2 and RB(OH)2 with elimination of H2 and H2O.
404 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415
Scheme 39. Reactions of L1AlH2 with diphenylsilanediol, phosphonic acids, and
pyrocatechol.
In 2004, the formation of a pentacoordinated tert-butylperoxo
aluminum compound 103 was accomplished via the reaction of
L1AlH2 (35) with t-BuOOH (Scheme 40) [99]. Notably, the structure
of compound 103 has two four-membered Al2O2 rings and each
aluminum atom is five-coordinated. However, the mechanism of
this reaction was not studied. A series of aluminum compounds
containing the CAOAAlAOAC framework (104–107) were pre-
pared by reacting one equiv. of L1AlH2 (35) with two equiv. of alco-
hols and phenols, respectively in toluene/THF at 0 °C with the
elimination of two equiv. of H2 [100,101]. Moreover, the similar
reactions with the elimination of H2 were accomplished to yield
an unusual aluminum Schiff base 109 with a C3NAlO six- and a
C2NAlO five-membered ring, sharing the same N ? Al coordinate
bond [102] and a basket-like molecule 108 with the C4S2 unit as
the bottom part and O2Al as the handle [101] (Scheme 40). Accord-
ing to the synthesis of compounds 104, 106 and 107, L1AlH2 prefers
Scheme 40. Reactions of L1AlH2 with molecules containing the functional –OH and –COOH groups to afford novel aluminum compounds.
Fig. 23. The X-ray single crystal structure of compound 108 with a basket-like
moiety.
to react preferentially with –OH than –NH2, due to the higher AlAO
bond energy of the resulting products. The composition of the
complex 108 was confirmed by means of single-crystal X-ray
structural analysis (Fig. 23).
The stoichiometric reactions of LAlH2 with amines were inves-
tigated with the result of different structures (Scheme 41). A mix-
ture of equal amounts of L1AlH2 and ArNH2 in the absence of
solvent was treated at 150 °C until H2 evolution ceased affording
L1AlH-(NHAr) (110) [50]. A series of aluminum heterocyclic ring
compounds 111–113 were synthesized by reacting L1AlH2 with
functionalized benzene rings (–NH2, -SH) and MeNHNH2, respec-
tively in the presence of a solvent [101–103]. The formation of
113 shows the simultaneous reaction of the –SH and –NH2 groups
to generate the expected five-membered AlNC2S ring.
Recently, Masuda and coworkers reported the reaction of LAlH2
with sterically bulky phenols Ar OH (Ar = 2,4,6-Me3C6H2 or
2,6-iPr2C6H3) to get compounds of composition LAl(H)OAr (116
and 117). Meanwhile, they also reported that LAlH2 reacted with
‘‘wet” N-hydroxylamine (TEMPO-H) to form L-Al(H)TEMPO (114)
and L-Al(OH)TEMPO (115). However, when LAlH2 reacts with
anhydrous TEMPO-H, the only product which is formed is L-Al(H)
TEMPO (114) (Scheme 42) [104].
 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415
Scheme 41. Preparation of compounds 110–113.
Scheme 42. Reactions of L1AlH2 with TEMPO-H.
4.2.4. Reactions between NacNacAlH2 and unsaturated compounds
Normally, aluminum hydrides are common stoichiometric
reducing reagents for unsaturated compounds containing C@X
(X = N, O, S), N@N, or C„N fragments, which could undergo vari-
ous reactions, such as (i) addition or reduction [105], (ii) displace-
ment or substitution [106], (iii) proton abstraction [107].
In 2004 Y. Peng et al. reported the reaction of L1AlH2 with an
excess of tert-butyl isocyanate in the presence of trace amounts
of water, which resulted in a terminal hydroxide containing a din-
uclear alumoxane L1Al(OH)OAlL1(OCH@N-tBu) (118) (Fig. 24)
[108]. In order to elucidate the formation of 118, the reaction of
L1AlH2 with t-Bu-N@C@O in a 1:1 ratio was conducted and
Fig. 24. The X-ray single crystal structure of compound 118.
405
resulted in L1AlH(OCH@N-t-Bu) (119), which further reacted with
another L1AlH2 molecule and two equiv. of water to yield com-
pound 118. Similar with the formation of compound 119, L1Al
(NHN@R) (R = CHSiMe, 120; N-1-Ad, 121) was prepared via inser-
tions of the N@N bond into the AlAH bond [109]. L1Al(NHN@N-1-
Ad) (121) was converted into the L1AlNH-1-Ad(NH-N@N-1-Ad)
(122) and L1Al(NH-1-Ad)2 (123), respectively with elimination of
N2. The possible mechanism was proposed that two molecules of
N@N@N-1-Ad inserted into the two AlAH bonds of L1AlH2 to
obtain the L1Al(NHN@N-1-Ad)2 (121). The latter undergoes 1,3-H
migration, and successively resulted in the desired products 122
and 123, respectively (Scheme 43).
L1AlH2 (35) reacted with one or two equiv. of benzaldehyde
under insertion into the AlAH bonds affording the desired products
L1AlHOBz (124) and L1Al(OBz)2 (125), respectively [93] The steri-
cally bulky benzophenone was also explored to successfully pre-
pare the L1AlHOCHPh2 (126) (Scheme 44). The reaction between
terminal alkynes with L1AlH2 resulted in the formation of
L1AlHC„CR (127) and L1Al(HC„CR)2 (128), respectively, due to
the equiv. ratio of reagents [110] (Scheme 44).
4.2.5. Reactions of NacNacAlH2 with further reagents
A series of compounds LAlX2 (X = Cl, Br, I) supported by the ster-
ically encumbered b-diketiminate ligands have been synthesized
and structurally characterized. Preferentially they are prepared
from the reaction of LLiOEt2 with AlX3 (X = Cl, Br) and by treat-
ment of LAlMe2 with I2. The first b-diketiminato aluminum com-
pound of composition L1AlF2 (129) was prepared in 2006 by
Singh et al. from the reaction of L1AlH2 with BF3OEt2 at low tem-
perature [111] (Scheme 45).
Recently, the reaction of b-diketiminato aluminum dihydrides
with N-aryl-substituted N-heterocyclic carbenes (NHCs) by CAN
bond activation to give aluminum amido-alkyl derivatives
[HC{(Me)-CNAr}2AlCH2(N(Ar0 )CH)2] was reported by Hill and
coworkers [112]. The generation of 1,3-bis(phenyl)imidazol-2-ylidene
in situ via deprotonation of the corresponding imidazolium
406 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

Scheme 43. Reactions of compounds containing N@C@O and N@N@C/N substituents, respectively, with L1AlH2 (35).

Scheme 44. Reactions of L1AlH2 with ketones and phenylacetylene.

tetrafluoroborate with KN(SiMe3)2 was followed with the facile ring

Scheme 45. The preparation of 129 from the reaction of the corresponding hydride
with BF3OEt2.
opening of NCH by LAlH2 at room temperature giving the correspond-
ing products [HC{(Me)-CNAr}2AlCH2(N(Ar0 )CH)2] (130 and 131).
Moreover, the LAlH2 (L = [CH(CMeNAr)2]
and Ar = 2,4,6-Me3C6H2)
reacted with NHC(IMes) directly to yield compound [HC{(Me)-
CNAr}2AlCH2(N(Mes)CH)2] (132), while the reaction of L1AlH2 with
IMes or IPr directly could not afford the desired compounds
(Scheme 46). The crystal structure of 130 is shown in Fig. 25.

Scheme 46. Synthetic routes to [HC{(Me)-CNAr}2AlCH2(N(Ar0 )CH)2].

 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415 407

Scheme 47. The synthesis of r-alane complexes of manganese and chromium.

b-diketiminato aluminum hydride has great potential in the

formation of various novel aluminum complexes, which have the
capability to function as important catalysts.

5. The synthesis, structure, and reactivity of

pentamethylcyclopentadienyl and its derivatives

5.1. The synthesis of (Cp*Al)4 and its derivatives

Fig. 25. The X-ray single crystal structure of 130. Pentamethylcyclopentadienyl (Cp*) ligand is an important sub-
stituent due to its steric bulk and electronic properties in coordina-
tion chemistry, and it is usually utilized to support p-block
4.2.6. Function as ligands for supporting transition metals
compounds with lower valent elements [23,24,119,120]. The first
The addition of transition metals to the b-diketiminato alu-
example of the organometallic Al(I) stabilized by Cp* (Cp* = g-
minum hydride has been accomplished to prepare r-complexes
C5Me5) was reported by Schnöckel and co-workers in 1991 [121].
with the Al–H–M framework, which is a reaction of fundamental
(Cp*Al)4 was obtained from the reaction of metastable AlCl with
importance to catalysis. In 2012, Aldridge and coworkers generated
Cp*2Mg at low temperatures (Scheme 48). Compound 135 is stable
manganese r-alane complex (133) (Fig. 26) and chromium r-alane
in the solid state under normal conditions and remains its tetrameric
complex (134) via the reactions of L1AlH2 with Cp0 Mn(CO)3
structure in solution. At temperatures above 30 °C in solution there
(Cp0 = CH3Cp) and Cr(CO)6, respectively, under photolytic condi-
exists an equilibrium between tetrameric (Cp*Al)4 and monomeric
tions [113] (Scheme 47). Finally, further studies of r-alane
Cp*Al [122,123]. The latter was also determined as monomer in
complexes featuring LAlH (L = HC(CRNAr)2) have been reported
the gas phase by electron diffraction [124]. However, the synthesis
by Aldridge [114] and Crimmin [115–117]. A relevant review was
and storing of AlCl is rather difficult as it was prepared from the
also reported [118].
reaction of HCl with Al at 1200 K [125]. Hence in the following years,
In conclusion b-diketiminato aluminum hydride LAlH2 could
many facile methods for the synthesis of (Cp*Al)4 were accomplished
work as precursor for the design and synthesis of many novel
by Roesky et al. The (Cp*Al)4 was obtained via the reduction of
aluminum compounds and also function as efficient catalyst in
Cp*AlCl2 with a small excess of potassium [126] and subsequent
hydroboration and dehydrocoupling. Although widely studied,
modifications were accomplished via the use of Na/K alloy as
reducing agent or employing different Cp*AlX2 (X = Br, I) halides as
starting materials [127]. Since then, numerous investigations on
the synthesis of cyclopentadienylaluminum(I) derivatives (RAl)4
have been accomplished, while R is the critical factor determining
the stability of (RAl)4. Therefore only few tetramers are known with
bulky substituents on aluminum. [(t-Bu)3SiAl]4 [128], [(Me3Si)3SiAl]4
[129] and asymmetric Cp*3Al3AlN(SiMe3)2 [123] were synthesized by
Schnöckel and co-workers via the reaction of AlX (X = Cl, Br, I) with
MR (M = alkali metal, R = Cp* substituents), respectively. In 1998, the
first aluminum(I) tetramer with r-bonded alkyl groups
[(Me3Si)3CAl]4 was synthesized by Roesky and coworkers via the
reduction of [(Me3Si)3CAlI2THF] by Na/K alloy in toluene [130].
Subsequently the group synthesized the first exclusively N-based
[2,6-iPr2C6H3N(SiMe3)Al]4 (136) employing the [2,6-iPr2C6H3N
(SiMe3)AlI2]2 as precursor [131] and the synthetic route is shown
in Scheme 49. In addition, [t-BuCH2Al]4 with neopentyl groups was
reported in 1991 [132] and [Al(C5Me4Ph)]4 was synthesized in
2005 [133].

5.2. The reactivity studies of (Cp*Al)4 and its derivatives

The reactivity studies of (Cp*Al)4 and its derivatives were

carried out with numerous reagents to obtain novel aluminum
Fig. 26. The X-ray single crystal structure of 133. compounds. (Cp*Al)4 was treated with an excess of selenium and
408 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

Scheme 48. Synthesis of tetrameric Al(I) compound.

Scheme 49. Synthetic route of [2,6-iPr2C6H3N(SiMe3)Al]4.

tellurium under mild conditions affording the heterocubane com-
pounds [Cp*AlSe]4 (137) and [Cp*AlTe]4 (138), respectively [126].
Both compounds are extremely sensitive to air and moisture,
which will lead to the decomposition with the formation of H2Se
and H2Te. In 2016, the treatment of (Cp*Al)4 with lighter chalco-
gens, like dioxygen, N2O, or sulfur to give the corresponding com-
plexes [Cp*AlX]4 [X = O (139) and S (140)]. This approach was
carried out by Braun, Kaupp, and coworkers [134]. Computational
comparisons of the Al clusters [Cp*AlE]4 (E = O, S, Se, and Te),
[AlCp]4 (Cp = g-C5H5), and [AlCp*]4 demonstrate the importance
of noncovalent interactions (NCI) in these compounds. In addition,
compound 141 with an unusual P4Al6 cage structure could be
obtained in high yield via reacting (Cp*Al)4 with elemental P4,
which proceeded under cleavage of the P4 tetrahedron into four
P building units [135]. These reactions are shown in Scheme 50
and structures of [Cp*AlSe]4 (137) and compound 141 with a
P4Al6 cage are placed in Figs. 27 and 28.
In 1994, Roesky and coworkers prepared the first dimeric imi-
noalane containing an Al2N2 heterocycle via treatment of (Cp*Al)4
with Me3SiN3 in a molar ratio of 1:4. The central core of compound
142 is a four-membered, almost ideally planar Al2N2 ring. The alu-
minum and nitrogen atoms are three-coordinate. 142 (Fig. 29) was
obtained from an Al4N4 cube, in which the top layer is broken open
and the remaining Al4N4 ring represents the base. A silyl-group
migration and a rearrangement of a Cp* group take place simulta-
neously. While the dimeric iminoalane (Cp*AlNMes)2 was not
obtained via the reaction of (Cp*Al)4 with MesN3 (Mes = Me3C6H2),
leading to the cyclic aminoalane 143 as a result of CAH bond acti-
vation of the ortho-bonded methyl group and subsequent migra-
tion of the proton to the nitrogen atom [136]. The reactions of
(Cp*Al)4 with Me3SiN3 and MesN3 are shown in Scheme 51.
The oxidative addition of organic azides to (Cp*Al)4 resulted in
the dimeric iminoalanes [(Cp*AlNSi(i-Pr)3]2 (144), (Cp*AlNSiPh3)2
(145), and [Cp*AlNSi(t-Bu)3]2 (146), respectively with elimination

Fig. 27. The X-ray single crystal structure of [Cp*AlSe]4 (137). Fig. 28. The X-ray single crystal structure of compound 141 with a P4Al6 cage.
 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415 409

Scheme 51. The reactions of (Cp*Al)4 with MesN3 and Me3SiN3.

Fig. 29. The X-ray single crystal structure of 142.

of nitrogen at temperatures between 50 and 75 °C in toluene. The

latter reactions were carried out by Roesky and coworkers in 1996
[137]. In 1998, another oxidative addition of MesN@CH–CH@NMes
(Mes = mesityl) to (Cp*Al)4 was conducted resulting in the mono-
meric aluminum(III) derivative 147 [138]. Compound 147 is the
Scheme 52. The oxidative additions of azides and MesN@CHACH@NMes (Mes =
first example of a monomeric aluminum diazabutadiene complex. mesityl) to (Cp*Al)4.
The two oxidative additions are shown in Scheme 52.
Treatment of (Cp*Al)4 with an excess of Ph2SiF2 under reflux for
three days resulted in the formation of cage complex 148, and the
X-ray single crystal structure of 148 is shown in Fig. 30. The syn- and (t-Bu)3Sb, and elemental antimony and other decomposition
thetic route was proposed that aluminum atom of the [Cp*Al] is products were formed as well. In 1996, Schnöckel synthesized
inserted into the SiAF bond. Meanwhile the reaction of (Cp*Al)4 compound As2(AlCp*)3 (150) with a polyhedral As2Al3 framework
with (t-BuSb)4 in toluene in a molar ratio of 1:1 at 60 °C was car- via reacting (Cp*Al)4 with (t-BuAs)4 in toluene in a molar ratio of
ried out resulting in a composition of [(Cp*Al)3Sb2] (149) [139]. 1:1 [140]. Along with the formation of As2(AlCp*)3, 2-
Note, the reaction was not stoichiometric with respect to 149 methylpropane and isobutene were also obtained. The similar

Scheme 50. The reactions of (Cp*Al)4 with O2 (N2O), Se, Te, and P4, respectively.
410 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

Scheme 55. Reaction of (Cp*Al)4 with [(dcpe)Pt(H)(CH2t-Bu)] (dcpe = bis(dicyclo-

hexylphosphino)ethane).

Fig. 30. The X-ray single crystal structure of 148.

reaction of (Cp*Al)4 with (t-BuP)3 was investigated to give the first

four-membered Al/P-ring compound 151 [141]. This consists of a
folded four-membered AlP3-ring with alternating Al-P-positions
(Scheme 53). Fig. 31. The X-ray single crystal structure of compound 159.

Scheme 53. The reactions of (Cp*Al)4 with further reagents.

Scheme 54. Synthesis of compounds 153–158.

 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415 411

Scheme 56. Synthesis of compounds 160–163.

Scheme 57. Synthesis of mixed-metal clusters 164–166 and byproduct 167.

Fig. 32. The X-ray single crystal structure of compound 164.

412 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

5.3. Function as ligand in coordination chemistry
5.3.1. Main-group metal complexes
In 2000, compound [Cp*Al-B(C6F5)3] (152) with the first exam-
ple of an aluminum(I)-boron donor–acceptor bond was synthe-
sized by Cowley and co-workers [142]. The adduct was obtained
by the addition of toluene to a mixture of (Cp*Al)4 and B(C6F5)3.
It is noteworthy that (Cp*Al)4 works as a pure donor ligand with
no backbonding. Then the reactivity of highly Lewis acidic perfluo-
rinated borafluorene C12F8BR (R = C6F5, CH3) and the nonfluori-
nated 9-phenyl-9-borafluorene towards (Cp*Al)4 was explored
and afforded g1 Lewis acid-base adducts 153–155 [143]. A DFT
computational study was conducted to probe the reason for the
strong preference for g1 bonding, which essentially stems from
the localization of aromaticity in the flanking phenyl rings in the
9-borafluorene ring system (Scheme 54). Additionally, compound
[Cp*Al-Al(C6F5)3] (156) was obtained in 2001, which is the first
valence isomer of a dialane [144]. As the similar synthetic proce-
dure, 13-group-13 donor–acceptor complexes [Cp*Al-Al(t-Bu)3]
(157) and [Cp*Al-Ga(t-Bu)3] (158) were also synthesized by Schulz
and co-workers from the reactions between (Cp*Al)4 with M(t-Bu)3
(M = Al, Ga), and [Cp*Al-Ga(t-Bu)3]. The latter is the only example
where the EI element has a lower atomic number than the EIII
acceptor element [145]. The synthetic routes of compounds 153–
158 are shown in Scheme 54.

Fig. 33. The X-ray single crystal structure of 166. Fig. 34. The X-ray single crystal structure of 168.

Scheme 58. Synthesis of some mixed metal clusters 168–173.

 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415
Fig. 35. The X-ray single crystal structure of [{Cp*Ru}3(l-H)5(l3-AlCp*)] (170).
5.3.2. Transition metal complexes with Cp*Al as ligand
The (Cp*Al)4 is considered as potent and exotic ligand in coordi-
nation chemistry, especially the bonding to transition metals. A
number of chemists contributed to the synthesis of numerous inter-
esting compounds starting from (Cp*Al)4. Among these chemists,
Fischer and coworkers have made contributions to the formation
of coordination compounds of AlCp* to transition metal centers. In
2000, the treatment of [(dcpe)Pt(H)(CH2t-Bu)] (dcpe = bis(dicyclo
hexylphosphino)ethane) with Cp*Al afforded the first phosphine-
substituted transition metal complex 159 with terminal coordi-
nated Cp*Al ligand (Scheme 55) [146]. The structure of the complex
159 was confirmed by single crystal X-ray structural analysis
(Fig. 31). DFT calculation on compound 159 was carried out verify-
ing the rather weak PtAAl bonds. In 2004, a series of products 160–
162 was obtained with transition metals (Scheme 56) [147]. The
solvent is the vital factor in the reaction of intermediate [Ni(Cp*Al)3]
with (Cp*Al)4 to give the different products 160 and 162. In 2005,
following the similar method, another coordination compound of
AlCp* to d10 metal center: [Pd(AlCp*)4] (163), along with [Ni
(AlCp*)4] (160) were obtained via the reactions of (Cp*Al)4 with
[(tmeda)PdCl2] and [Ni(cod)2] in a molar ration of 5:1 and 4:1,
respectively (Scheme 56) [133]. Note that [Ni(AlCp*)4] and analo-
gous compound [Ni(AlCp*)2(PPh3)2] could react with 1 equiv. of
Scheme 59. Synthesis of lanthanide/actinide-metal complexes with Cp*Al as ligand.
413
[FeCp2][BArF4] resulting in two uncommon NiI cationic complexes
in high yields [148]. Fischer et al. presented a series of homoleptic,
mixed-metal clusters 164–166 with di- and trinuclear palladium
and platinum cores and ECp* (E = Al, Ga, In) as stabilizing ligand.
Complexes with the AlCp* ligand are shown in Scheme 57 and
X-ray single crystal structures of 164 and 166 are placed in Figs. 32
and 33. Furthermore, ligand exchange reactions of these cluster
complexes are explored [149]. A series of novel mixed metal clus-
ters 168–173 with transition metals and Cp*Al are reported [150–
153] (Scheme 58). The X-ray single crystal structures of 168 and
170 are shown in Figs. 34 and 35. Additionally, the Fischer group
utilized Co-hydrogenolysis of (AlCp*)4 with [CpCu(PMe3)] to syn-
thesize CuAl2 and a/b-CuAl colloids [154]. Another route to b-
CoAl and b-CoAl/Al nanoparticles started from (Cp*Al)4 and was
explored by Fischer et al. [155].
In 1998, the polyhedral Al2Co2 cluster (l-Cp*Al)2Co2(CO)6 was
obtained by the reaction of (Cp*Al)4 with Co2(CO)8 in toluene at
60 °C by Schnöckel et al. [155]. The bonding description as a poly-
hedral Al2Co2 cluster is based on X-ray data as well as on DFT cal-
culations. In the polyhedral Al2Co2 cluster, AlCp* has completely
lost its original carbene like character, The substitution of olefin
ligands like cyclooctene (COT) on heteroleptic carbonyl complexes
was observed in the formation of Cp*AlCr(CO)5 starting from
(Cp*Al)4 and Cr(CO)5COT [156]. This result reflects the strong
reducing ability of Cp*Al with the consequence of a shift of the
electron density towards the Cr atom and the CO ligands.
Treatment of a 1:4 mixture of (Cp*Al)4 and solvent free
[(g -C5Me5)2Ln] (Ln = Eu, Yb) [157–159] at 120 °C for several days
5
was carried out leading to red [(g5-C5Me5)2Eu-Al(g5-C5Me5)] (174)
and green [(g5-C5Me5)2Yb-Al(g5-C5Me5)] (175) in moderate yields
(Scheme 59) [160]. Both products are very air sensitive and
decompose quickly in aromatic solvents. In 2008, Arnold et al. syn-
thesized the first example of an unsupported bond between an
actinide and group 13 element of composition (CpSiMe3)3U-AlCp*
(176) [161]. DFT calculation was conducted to suggest that the
UAAl bond exhibits some covalent character owing to charge
transfer from the Cp*Al ligand onto uranium. Soon afterwards a
series of similar compounds of composition (CpSiMe3)3M
ECp*
(M = Nd, U, Ce; E = Al, Ga) were reported (Scheme 59) [162,163].
In conclusion, due to their similarity to N,N chelating sub-
stituents, numerous compounds have been synthesized starting
from (Cp*Al)4, including the activation of small molecules or
functioning as ligands to main group and transition elements.
Furthermore, many theoretical investigations have also con-
tributed to understand the structures and properties of (RAl)4
in transition metal complexes [164–166]. This is an open field
for many investigations to study the application of these coordi-
nation complexes.
414 Y. Liu et al. / Coordination Chemistry Reviews 374 (2018) 387–415

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