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This paper is published as part of a Dalton Transactions theme issue:

Dalton Discussion 11: The Renaissance of Main Group

Chemistry
Guest Editor: John Arnold
University of California, Berkeley, CA, USA
23 - 25 June 2008

Published in issue 33, 2008, of Dalton Transactions

Published on 24 July 2008 on http://pubs.rsc.org | doi:10.1039/B801400K
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Image reproduced with permission of Manfred Scheer

Papers published in this issue include:

The coordination chemistry of group 15 element ligand complexesa developing area

Manfred Scheer, Dalton Trans., 2008 DOI: 10.1039/b718179p

Formation, structure and bonding of metalloid Al and Ga clusters. A challenge for chemical efforts
in nanosciences
Hansgeorg Schnckel, Dalton Trans., 2008 DOI: 10.1039/b718784j

Polymeric materials based on main group elements: the recent development of ambient
temperature and controlled routes to polyphosphazenes
Vivienne Blackstone, Alejandro Presa Soto and Ian Manners, Dalton Trans., 2008
DOI: 10.1039/b719361k

Recent developments in the chemistry of low valent Group 14 hydrides

Eric Rivard and Philip P. Power, Dalton Trans., 2008 DOI: 10.1039/b801400k

Chemistry and physics of silicon nanowire

Peidong Yang, Dalton Trans., 2008 DOI: 10.1039/b801440j

Visit the Dalton Transactions website for more cutting-edge inorganic and organometallic research
www.rsc.org/dalton
 PERSPECTIVE
Recent developments in the chemistry of low valent Group 14 hydrides
Eric Rivard and Philip P. Power*
Received 25th January 2008, Accepted 3rd March 2008
First published as an Advance Article on the web 24th July 2008
DOI: 10.1039/b801400k
This Perspective discusses the synthesis and reactivity of low valent Group 14 hydrides of germanium
and tin. The use of hindered terphenyl ligands has facilitated the isolation of a number of unusual new
Published on 24 July 2008 on http://pubs.rsc.org | doi:10.1039/B801400K
main group hydride structural types (each predicted by computational work), and has culminated in the
use of these species as precursors to new cluster archetypes.
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1. Introduction
Main group metal hydrides are of practical interest as a result of
their widespread use in synthetic organic chemistry,1 and their em-
ployment as precursors for high-purity element and alloy devices
for the electronics industry.2 In the case of Group 14 hydrides,
examples of stable hydrides had been restricted to derivatives of
the tetravalent elements.3 This situation changed in 2000 when it
was shown that the divalent tin(II) hydride (Ar*SnH)2 could be
prepared by using the sterically encumbered Ar* ligand (Ar* =
C6 H3 -2,6-(C6 H2 -2,4,6-i Pr3 )2 ).4 In addition, Lewis base stabilized
divalent Group 14 element hydrides have been reported.5 These
successes were largely made possible through the development
of new hindered ligands which encourage the formation of low
coordinate environments at the reactive main group centers.6
In this Perspective, we discuss some of our recent work in the
area of low valent Group 14 hydrides with particular focus on their
synthesis, structure and newly uncovered reactivity.
Department of Chemistry, University of California, Davis, One Shields Ave.,
Davis, California, USA 95616. E-mail: pppower@ucdavis.edu
Based on the presentation given at Dalton Discussion No. 11, 2325 June
2008, University of California, Berkeley, USA.
Eric Rivard and Philip P. Power
4336 | Dalton Trans., 2008, 43364343
www.rsc.org/dalton | Dalton Transactions
2. Synthesis of low valent germanium(II) and tin(II)
hydrides
The chemistry of divalent Group 14 element derivatives has now
reached a stage of maturity with numerous well-dened examples
of stable monomeric carbenes, silylenes, germylenes, stannylenes
and plumblylenes (R2 E:; E = CPb) now known.7 In comparison,
much less is known about their hydride analogues where at least
one of the substituents is replaced by hydride functionalities.8
As shown below, the use of bulky terphenyl ligands enables the
isolation of these once elusive species.
The synthesis of a stable tin(II) hydride derivative proved to be
straightforward once ligands of sufcient bulk became available.9
As shown in Scheme 1, treatment of the terphenyl tin(II) chloride,
Ar*SnCl, with Li[AlH4 ] proceeded cleanly to give the target
tin(II) hydride, (Ar*SnH)2 (1), as a deep orange solid. Compound
1 crystallized as a centrosymmetric dimer that is associated
through a pair of SnHSn bridges. This species represented the
rst example of a low valent Group 14 hydride derivative that
was isolable at room temperature, in contrast to less crowded
derivatives which can be studied only by matrix isolation or high
vacuum techniques.8a,b
Our initial investigations of the chemistry of the corresponding
low valent germanium hydrides, started from the stable organoger-
manium(II) chloride (Ar GeCl)2 , Ar = C6 H3 -2,6-(C6 H3 -2,6-i Pr2 )2
Eric Rivard received his BSc in Chemistry from the University
of New Brunswick and his PhD from the University of Toronto.
After post-doctoral work at Caltech, he moved to the University of
California at Davis to on low valent Group 14 hydrides and clusters
and is currently at Monash University. Beginning in August 2008,
he will be a faculty member at the University of Alberta.
Philip Power received a BA from Trinity College Dublin and a
DPhil from the University of Sussex. After post-doctoral studies at
Stanford University he joined the Department of Chemistry at the
University of California, Davis, where he is Professor of Chemistry.
His main interests lie in the exploratory synthesis of new main group
and transition metal complexes. A major theme of his work has been
the use of sterically crowded ligands.
This journal is The Royal Society of Chemistry 2008

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Scheme 1 Synthesis of Ge(II) and Sn(II) hydrides and the attempted
preparation of a Pb(II) hydride.
(Scheme 1). Following a similar protocol as used in the synthesis
of (Ar*SnH)2 ,4 (Ar GeCl)2 was treated with a variety of hydride
sources such as Li[AlH4 ], LiH, NaH or DIBAL (i Bu2 AlH).
However instead of isolating the desired germanium(II) hydride,
the colorless germanium(IV) hydride, Ar GeH3 was obtained as the
major product. Fortunately, use of the milder reducing agent L-
selectride (Li[s Bu3 BH]) afforded a stable germanium(II) hydride
dimer, (Ar GeH)2 (2) as a highly air- and moisture sensitive
orange solid in moderate yield. This species was structurally
distinct from its tin counterpart in that it was GeGe bonded
having terminal GeH bonds and trans-pyramidalized geometry
at the germaniums.10 Compound 2 displayed signicant thermal
stability when held in a protective atmosphere of nitrogen, and
melted without noticeable decomposition at a temperature of
123 C. High thermal stability is a general feature of compounds
that have terphenyl-based co-ligands and is a powerful indicator
of the utility of such ligands in providing the necessary kinetic
stabilization of reactive chemical environments.
When 2 was generated in the presence of excess PMe3 , the un-
usual mixed-valent germanium hydride, Ar (H)2 GeGeAr (PMe3 )
(3) was isolated as a yellow crystalline solid.10 In this reaction,
the binding of PMe3 to one of the germanium centers leads
to a novel hydrogen displacement reaction, and generation of
formal oxidation states of +1 and +3 for the phosphine-bound and
hydride-rich germanium centers in 3, respectively. This asymmetric
hydride structure will surface again when the structural versatility
that exists within terphenyl tin(II) hydrides is discussed.
Attempts to prepare an analogous divalent lead(II) hydride led
to a considerably different result. When Li[AlH4 ] was combined
with Ar*PbBr in benzene, well-formed amber-green dichroic
crystals were obtained which were later identied as the diplumby-
lyne Ar*PbPbAr* (4).11 The serendipitous formation of 4 was
an important discovery as this compound represented the rst
example of a stable heavy Group 14 element alkyne analogue.12 The
formation of the Pb(I) dimer 4 could involve the initial generation
of a putative lead(II) hydride intermediate, Ar*PbH, which rapidly
eliminates H2 to form the observed product. This form of a
dehydrocoupling reaction is commonly observed throughout the
This journal is The Royal Society of Chemistry 2008
main group.13 Perhaps with a judicious choice of co-ligand, an
example of a stable Pb(II) hydride might be prepared in the future.14
3. Structural and spectroscopic features
Before the structural and spectroscopic details of low valent Group
14 hydrides are discussed in more detail, it is worthwhile to
comment on the possible isomeric forms that are available to
mono-substituted tetrel(II) hydrides (Chart 1). Although this eld
is still in its infancy, examples of forms I and III (phosphorus
stabilized) have been structurally authenticated for germanium,10
while for tin there is a greater tendency for the formation of
bridging EHE linkages, and compounds with structures related
to forms III and IV are now known.15 Theoretical studies on the
parent species, H2 GeGeH2 , have shown that form I is the most
stable isomer of the series, while for the parent tin dimetallene,
H2 SnSnH2 , isomeric forms IIV all lie within 10 kcal mol1 of each
other.8c,15 This suggested the possibility that control of the stability
of the various isomers might be attainable by suitable modication
of the steric and electronic nature of the ligand bound to tin.
Chart 1 Possible structural forms available to substituted Group 14
(tetrel) hydrides.
Germanium(II) hydrides
In line with the theoretical data presented above, the germy-
lene hydride dimer, (Ar GeH)2 2 has a pyramidal dimetallene
arrangement in the solid state (Fig. 1) in which the terphenyl
ligands are located trans to each other (analogous to form I in
Chart 1).10,16 The GeGe distance in 2 is 2.3026(3) A and is within
the range of 2.212.46 A typically observed in disubstituted Ge(II)
digermenes, R2 GeGeR2 .17 In addition, there exists signicant lone
pair character at each Ge center as reected by the bending
of the HGeCipso array out of planarity by 45.0 . Consistent
with the presence of terminal GeH bonds in 2, well-dened
IR bands were located at 2060 and 2100 cm1 ; for comparison,
Ge(IV)H stretching bands are usually observed in the range 1900
2000 cm1 .18
Addition of the strong r-donor PMe3 to 2 induces a structural
change to give the mixed-valent species 3 (eqn (2) and Fig. 2). This
species shows numerous structural differences in comparison to
its parent 2. For example, the GeGe distance in 3 is much longer
[2.5304(7) A] and is consistent with the presence of a weakened Ge
Ge single bond. In addition, the intraligand angles at germanium
become narrower upon the binding of PMe3 , with Cipso GeGe
angles of 101.49(7) and 119.80(8) at the phosphine- and hydride-
bound Ge centers, respectively; the related CGeGe angle in 2 is
121.93(4) . The IR spectrum of 3 yielded an absorption centered
Dalton Trans., 2008, 43364343 | 4337
Published on 24 July 2008 on http://pubs.rsc.org | doi:10.1039/B801400K

Fig. 3 Molecular structure of 1. Reprinted with permission from ref. 4.

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Copyright 2000 American Chemical Society.

Fig. 1 Molecular structure of 2. Reprinted with permission from ref. 16.
Copyright 2005 American Chemical Society.
preparation of a number of new tin(II) hydride species featuring
sterically, and possibly electronically, distinct ligands. Scheme 2
outlines the various tin(II) hydrides that were prepared along with
their solid state structures.15 In order to prepare the less-hindered
tin hydride, (Ar SnH)2 (4a) an amide/hydride transmetallation
route was also used (eqn (4)), as the direct reduction of Ar SnCl to
4a with various hydride reagents gave signicantly lower product
yields. In the case of the 4-X-Ar derivatives (orange solids), similar
centrosymmetric structures as 1 were found in the solid state with
SnSn separations in the range 3.0532(8)3.1176(11) A (see Fig. 4
for a representative structure).
The addition of two i Pr groups at the meta positions of the
central ring of the Ar* ligand yielded the new ligand, 3,5-i Pr2 -
Ar* (Scheme 2), whose steric properties are considerably different
from pre-existing sterically crowding terphenyl ligands.22 As shown

Fig. 2 Molecular structure of 3. Reprinted with permission from ref. 10.

Copyright 2003 American Chemical Society.

at 1905 cm1 that was assigned to the terminally bound GeH

groups.

Terphenyl tin(II) hydrides

In 2000, we reported the rst example of a stable divalent Group 14

element hydride, (Ar*SnH)2 (1).4 As depicted in Fig. 3 compound
1 crystallized as a centrosymmetric dimer with accompanying Sn
HSn bridging interactions; recently the structure of 1 was also
examined by neutron diffraction which conrmed the overall accu-
racy of the structure and the bridging positions of the hydrogens.19
Key structural features of 1 include a long Sn Sn separation of
3.1260(11) A which is longer than a typical SnSn single bond (ca.
2.762.88 A),20 and highly pyramidalized coordination at the tin
centers [e.g. Cipso SnSn angle = 98.11(15) ].
Motivated by prior theoretical studies which show minimal
energy differences between the various tin(II) hydride isomers
related to forms IIV in Chart 1, we decided to attempt the Scheme 2 Preparation of various terphenyl tin(II) hydride derivatives.

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Fig. 4 Molecular structure of 4a.21
in eqn (5), reduction of the tin(II) chloride {[3,5-i Pr2 -Ar*]SnCl}2
with DIBAL gave a deep-blue compound which was identied as
the asymmetric mixed-valent species, [3,5-i Pr2 -Ar*]Sn(H)2 Sn[3,5-
i
Pr2 -Ar*] (5). Due to the quality of the crystals, we were unable to
locate the tin-bound hydrogen atoms directly by crystallography.
However, by using a combination of NMR and Mossbauer
spectroscopies, and high-level theoretical calculations, a mixed-
valent structure could be assigned with condence to 5 wherein
two hydrogen atoms are bound to one of the tin centers [i.e. Sn(1)
in Fig. 5].
Fig. 5 Molecular structure of 5. Reprinted with permission from ref. 15.
Copyright 2007 American Chemical Society.
Examination of the X-ray structure of 5 revealed the presence of
an SnSn distance [2.9157(10) A] that was ca. 0.150.20 A shorter
than that found in the previously known tin(II) hydrides 1 and
4.15 This SnSn separation is indicative of the presence of a long
SnSn single bond, while wide SnSnC angles of 126.44(15)
and 106.37(17) were present at Sn(1) and Sn(2), respectively. The
assignment of two hydrogen atoms to Sn(1) was corroborated by
theoretical models which place hydrogen atoms at the tin center
This journal is The Royal Society of Chemistry 2008
with the widest CSnSn angle. Mossbauer spectroscopy revealed
that two distinct tin environments were present in 5 with the
divalent tin center, labeled Sn(2) in Fig. 5 and site B in Fig. 6,
giving a resonance at 3.252(7) mm s1 with a large quadrupolar
splitting parameter of 3.713(7) mm s1 . The remaining tin site,
Sn(1) [site A; Fig. 6], was more symmetric due to the presence of
two bound H atoms, and gave a resonance with an isomer shift of
1.370(4) mm s1 with an expectedly smaller quadrupolar splitting
parameter of 0.967(4) mm s1 .15
Fig. 6 Mossbauer spectrum of 5. Reprinted with permission from ref. 15.
Copyright 2007 American Chemical Society.
Compound 5 displayed a SnH resonance at 7.92 ppm in the 1 H
NMR spectrum with well-resolved SnH satellites due to coupling
with the 117/119 Sn nuclei (I = 12 ; abundance of ca. 8% each). From
these anking satellites, an average 1 J SnH coupling constant of
ca. 528 Hz was determined. Interestingly, organotin(IV) hydrides
generally yield much larger values of 1 J SnH where constants
approaching ca. 1900 Hz have been observed.23 The NMR and
IR spectral signatures of the mixed-valent species 5 differed
greatly from that of the centrosymmetric dimers 4. For the
hydride series 4, the SnH resonances in the 1 H NMR spectra
were signicantly shifted downeld to the narrow range of 9.11
9.28 ppm. Moreover, the accompanying tin satellites yielded very
small values of 1 J SnH which were consistently near 90 Hz. These
small SnH coupling constants, strongly suggested the retention
of centrosymmetric dimer forms for 4 in solution where SnH
Sn bridges are preserved. A plausible explanation for the smaller
values of 1 J SnH in 4 is that the SnH bonds in the SnHSn bridges
are weaker than the terminally bound SnH bonds in 5.15
The above results helped to explain an unusual observation
noted during our initial studies of (Ar*SnH)2 (1). As discussed
earlier, this species has a similar centrosymmetric dimer form
to those of 4a4d with symmetric SnHSn bridges. However
when 1 was dissolved in organic solvents, a deep blue solution
resulted which gave a SnH resonance at 7.87 ppm in the 1 H NMR
spectrum (1 J SnH = 592 Hz). This resonance was very similar to that
observed in the corresponding mixed-valent species 5. In addition,
both compounds 1 and 5 are dark blue in solution, while the
less-hindered hydrides 4 give very pale blue-green solutions upon
dissolving. Furthermore, compound 1 gave two SnH stretches
at 1771 and 1828 cm1 in the IR spectrum, while 5 had similar
absorptions at 1783 and 1810 cm1 ; signicantly, compounds 4a
4d, which preserve the SnHSn bridges in solution, display no IR
absorptions in the 15002800 cm1 region.15 These results strongly
suggest that while compound 1 has a centrosymmetric structure
(IV) in the solid state, it undergoes a structural change to the
Dalton Trans., 2008, 43364343 | 4339
 mixed-valent form III (Chart 1) in solution. These results highlight
the structural versatility that is inherent to tin(II) hydrides.
4. Reactivity
Alternate pathways to Group 14 hydrides
The synthetic strategies for the hydrides 15 presented above all
involve precursors that are in a +2 oxidation state (i.e. non-redox or
redox-invariant synthesis). However, in the course of explorations
into the reactivity of the heavy Group 14 dimetallynes Ar EEAr
(E = Ge24 and Sn25 ), oxidative routes towards germanium and tin
Published on 24 July 2008 on http://pubs.rsc.org | doi:10.1039/B801400K
hydrides were discovered.
For example it was found that the digermyne, Ar GeGeAr
(6), reacted spontaneously with H2 under ambient conditions
to give differing quantities of the oxidized germanium hydrides,
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Ar (H)GeGe(H)Ar (7), Ar H2 GeGeH2 Ar (8) and Ar GeH3 (9)
depending on the amount of hydrogen added (Scheme 3); com-
pounds 79 represent examples of germanium hydrides with
formal oxidation states at Ge of +2, +3 and +4, respectively.16 In
fact the direct addition of H2 to 6 represents the best route currently
available to prepare the Ge(III) hydride, 8. Although the activation
of H2 by transition-metal centers is well-known,26 the reaction
of H2 with Ar GeGeAr represented the rst well documented
reaction of H2 with a molecular main group compound under
ambient conditions.27 Some important recent breakthroughs in
this area have been reported by the groups of Stephan28 and
Bertrand.29
Scheme 3 Addition of dihydrogen to Ar GeGeAr (6) at room tempera-
ture. Reprinted with permission from ref. 16. Copyright 2005 American
Chemical Society.
The reactivity of Ar GeGeAr toward hydrogen was explained
on the basis that it had diradical character as illustrated in
Scheme 4.30
Scheme 4 Resonance forms of Ar GeGeAr .
This explanation has received support from computational
work.31 Reactivity studies of variously substituted dimetallynes
ArMMAr (M = Ge or Sn, Ar = variety of terphenyl ligands) with
H2 is currently underway and details of this work will be published
in the future.32
The addition of BH3 THF to Group 14 dimetallynes Ar EEAr
(E = Ge and Sn) also resulted in the formation of oxidized hydride
products. In the case of the digermyne, Ar GeGeAr , a complex
product mixture was obtained which contained the known hy-
drides, 79 (Scheme 5). In contrast, the related reaction with
Ar SnSnAr (10) generated the known tin(II) hydride (Ar SnH)2
4340 | Dalton Trans., 2008, 43364343
Scheme 5 Oxidative hydrogenation of Ar EEAr (E = Ge and Sn) by
BH3 THF.32
(4a) cleanly, and in high yield.32 Attempts to further oxidize 4a to
tin(III) or tin(IV) hydrides by treatment with excess borane led to the
recovery of unreacted 4a, thus highlighting the lower propensity
of Sn(II) centers to undergo oxidation relative to their Ge(II)
counterparts. The mechanism of the oxidative hydrogenation of
dimetallynes 6 and 10 is unclear at the moment and these reactions
are now being investigated in more detail.
Reduction of (Ar GeH)2 to give M2 [(Ar GeH)] (M = Li, Na and K)
Several examples of the reduction of tetrel(II) species such as
disilenes R2 Si=SiR2 , monomeric germylenes R2 Ge: or stannylenes
R2 Sn: by either alkali metals or electrochemical methods is
known.33 Such studies reveal important information with regard
to the bonding and electronic structure of these low valent
compounds.
In a similar manner to the above mentioned reports, the germa-
nium(II) hydride 2 was treated with excess Li powder or with Na or
K sand in toluene to give the highly reactive salts M2 [{Ge(H)Ar }]
(M = Li, Na or K; 1113) as deep-red/black crystals. As shown
in Fig. 7, the nature of the structural type formed depended
greatly on the alkali metal counterions. For example the potassium
salt 13 crystallized with a trans-pyramidal [Ar (H)GeGe(H)Ar ]2
core with terminal GeH bonds and a long GeGe distance of
2.6468(4) A; the related disodium salt contained a doubly reduced
GeGe core with bridging hydrogen atoms and concomitantly
long GeGe distance of 2.5904(5) A.34 The dilithium salt 11
has an overall structure which resembles that of 13 however the
germanium centers adopt a planar geometry with a much shorter
GeGe distance [2.395(2) A] that is close to the GeGe separation
in 2. It is not entirely clear why the GeGe distance in dilithio
derivative 11 is much shorter than in the potassium analogue,
however theoretical investigations have indicated that MGe
and Maryl interactions in 1113 could play an important role in
controlling the resulting GeGe bond length;34 similar interactions
have been identied between the Na and Al or Ga centers in the
related dialuminyne salt Na2 [Ar AlAlAr ] (14)35 or digallyne
Na2 Ar*GaGaAr*.36 Prior calculations by Trinquier have indicated
the bridged species HGe(l-H)2 H is a minimum on the potential
energy surface and lies only ca. 9 kcal mol1 higher than the lowest-
energy trans-pyramidal form H2 GeGeH2 .8c Therefore, in light of
this theoretical work, it appears that the corresponding dianions
[HGe(l-H)2 H]2 and [H2 GeGeH2 ]2 are also close in energy, and
that their structures can be interchanged by simply altering the
nature of the countercation present (as evidenced by compounds
12 and 13).
Tin cluster synthesis
This group and others have also been actively involved in the
preparation of new main group clusters. For the most part,
This journal is The Royal Society of Chemistry 2008
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Fig. 7 Structures of the salts of M2 [{Ge(H)Ar }] (M = Na and K; 12 and 13). Reprinted with permission from ref. 34. Copyright 2004 American
Chemical Society.

reductive methods involving alkali-metal based reagents such as

KC8 have been used to achieve the low oxidation states found
within the resulting element-rich clusters.37 However as more
low valent main group hydrides become available, these reactive
species are now being increasingly explored in the Power group as
precursors to novel main group clusters via thermolytic routes.
When a sample of (Ar*SnH)2 (1) was heated to 100 C in toluene,
the novel closo, tricapped, trigonal-prismatic cluster, Ar*3 Sn9 (15)
was isolated as deep red crystals in low yield (19%).38 Consistent
with a ligand stripping process, the arene byproduct, HAr*, was
also isolated from the mother liquor of the reaction medium
(Scheme 6, eqn (6)). Compound 15 is a paramagnetic cluster with
one unpaired electron (g = 2.031 by EPR spectroscopy) with an
overall structure which resembles that found in the corresponding
21-electron framework Zintl ion [Sn9 ]3 reported by Critchlow and
Corbett.39 As seen in Fig. 8, the Sn9 core is well-sheathed by the
three surrounding terphenyl ligands, and the SnSn bond distances
within 15 lie in the range 2.912(2)3.008(2) A (Fig. 8).

Fig. 8 Molecular structure of 15.38 A. F. Richards, B. E. Eich-

ler, M. Brynda, M. M. Olmstead and P. P. Power, Metal-Rich, Neutral
and Cationic Organotin Clusters, Angew. Chem., Int. Ed., 2005, 44, 2546.
Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with
permission.

during the synthesis of 16, indicating that cluster formation was

Scheme 6 Thermolytic syntheses of the tin clusters 15 and 16.
Replacement of the Ar* ligand by the less hindered Ar ligand led
to the isolation of a different cluster motif upon thermolysis of the
parent tin(II) hydride (Scheme 6, eqn (7)). Specically, thermolysis
of (Ar SnH)2 (4a) in hot toluene yielded the pentagonal bipyrami-
dal tin cluster, Ar 2 Sn7 (16) in modest yield as red-orange crystals
(Fig. 9). Unlike the Sn9 cluster 15, compound 16 was diamagnetic
and its 119 Sn NMR spectrum yielded two distinct signals at 530
and 420 ppm, which have been tentatively assigned to the tin
centers in the Sn5 core moiety, and the capping ArSn groups,
respectively. As in the case of 15, the arene, Ar H, was produced
accompanied by a ligand stripping process. The structure of 16
consists of a nearly ideal D5h symmetry within the Sn7 framework,
while the capping Ar groups deviate slightly from linearity. The
SnSn bond distances within the Sn7 unit [2.953.03 A] are similar
to those observed in 15, while the distance between the non-
bonded apical Sn centers, Sn(1) and Sn(2), is approximately 0.3 A
longer. Similar pentagonal bipyramidal structural motifs have
been observed within thallium-rich Zintl phases (in K10 Tl7 )40 , in
the mixed cluster [Pb5 {Mo(CO)3 }2 ]4 .41 Of note, application of
Wades rules to 16 leads to the prediction of 16 framework electrons
and a closo structure with seven vertices (n + 1 core electron pairs;
n = 7).42

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Fig. 9 Molecular structure of 16.21
The introduction of bulky amide ligands to tin cluster chemistry
has led to the recent synthesis of two large tin-rich clusters with
novel Sn15 cores. This work was carried out in collaboration
with Prof. Michael Lappert at the University of Sussex, and
a combination of traditional reductive methods and hydride
mediated syntheses were used to prepare the amide-capped
clusters [(DippNR)6 Sn15 ] (R = SiMe3 and SiMe2 Ph; 17 and
18).43 One route to 17 (Fig. 10) involved the treatment of
in situ generated ClSn[NDipp(SiMe3 )] with the hydride source,
Li[s Bu3 BH], at low temperatures, followed by subsequent warming
to room temperature. It is possible that an unstable tin(II) hydride,
HSn[NDipp(SiMe3 )], was rst generated which then participates
in cluster formation upon warming. We are currently trying
to synthesize stable examples of amido- and phosphido-tin(II)
Fig. 10 Molecular structure of 17.43 M. Brynda, R. Herber, P. B. Hitch-
cock, M. F. Lappert, I. Nowik, P. P. Power, A. V. Protchenko, A. Ruz-
icka and J. Steiner, High Nuclearity Group 14 Metalloid Clusters:
[Sn9 {Sn(NNR )}6 ], Angew. Chem., Int. Ed., 2006, 45, 4333. Copyright
Wiley-VCH Verlag GmbH & Co., KGaA. Reproduced with permission.
4342 | Dalton Trans., 2008, 43364343
hydrides by using more sterically encumbered amide and phos-
phide ligands.44
Conclusion
The use of hindered terphenyl ligands in the stabilization of low
valent Group 14 hydrides has led to a number of recent discoveries.
This work has uncovered striking structural versatility within
neutral and anionic species of the form [ArE(H)]2 x (E = Ge and
Sn; x = 0 or 2; Ar = terphenyl ligands). Furthermore the use of
tin(II) hydrides as precursors to tin-rich clusters yielded a variety
of new cluster archetypes. It is expected that future developments
in ligand design will lead to the production of increasingly exotic
cluster structures, and the synthesis of hitherto unknown species
such as a stable example of a organolead(II) hydride.
Acknowledgements
The authors would like to thank the National Science Foundation,
the donors of the Petroleum Research Fund, administered by
the American Chemical Society, and the U. S. Department of
Energy for nancial support. In addition, the authors are grateful
to the many co-workers named in the Reference section and to
Professors R. Herber, M. Head-Gordon and S. Nagase for crucial
collaborative work. E. R. is grateful to the Canadian government
for an NSERC postdoctoral fellowship.
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Downloaded by Cinvestav IPN on 11 September 2012
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Dalton Trans., 2008, 43364343 | 4343