From organotin hydrides to heteronuclear main group metal compounds: isolation of the first neutral bismuth/tin clusters

Article abstract of DOI:10.1039/d1cc02538d

From conversions of Ar₂SnH₂(Ar = Tripp, Dipp; Tripp = 2,4,6-Triisopropylphenyl, Dipp = 2,6-Diisopropylphenyl), and a bismuth(iii) amide, Bi[N(SiMe₃)₂]₃, we isolated the first representatives of mixed, uncharged Bi/Sn clusters, Bi₈Sn₃Ar₆. Along with unprecedented bicyclo[2.2.0]hexanes, (HAr₂Sn)₂Sn₂Bi₄, these have been characterized by single crystal X-Ray diffraction, heteronuclear NMR, vibrational and UV-Vis spectroscopy. Quantum-chemical calculations were carried out in order to understand bonding within the isolated polyhedral compounds.

Full text of DOI:10.1039/d1cc02538d

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: B. Steller, M. Flock
and R. C. Fischer, Chem. Commun., 2021, DOI: 10.1039/D1CC02538D.
Volume 54
This is an Accepted Manuscript, which has been through the
Number
January 2018
Pages 1-112
1
4
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 4
ChemComm
View Article Online
DOI: 10.1039/D1CC02538D
COMMUNICATION
From Organotin Hydrides to Heteronuclear Main Group Metal
Compounds: Isolation of the first neutral Bismuth/Tin Clusters
Beate G. Steller, a Michaela Flock a and Roland C. Fischer*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
From conversions of Ar2SnH2 (Ar = Tripp, Dipp; Tripp = 2,4,6- amides as an alternative strategy for cluster synthesis in
Triisopropylphenyl, Dipp = 2,6-Diisopropylphenyl), and a bismuth contrast to the more commonly used reductive and salt
(III) amide, Bi[N(SiMe3)2]3, we isolated the first representatives of metathesis reactions. Hydrostannolysis and -germolysis of
mixed, uncharged Bi/Sn clusters, Bi8Sn3Ar6. Along with organoelement(IV) hydrides and -amides have proven very
unprecedented bicyclo[2.2.0]hexanes, (HAr2Sn)2Sn2Bi4, these have useful for the synthesis of respective (alternating) oligo- and
been characterized by single crystal X-Ray diffraction, polymers.33-35
heteronuclear NMR, vibrational and UV-Vis spectroscopy. As an initial result, we herein report the first example of an
Quantum-chemical calculations were carried out in order to uncharged polyhedral Bi/Sn compound, Bi8Sn3Ar6, from the
understand bonding within the isolated polyhedral compounds.
conversion of Ar2SnH2 (Ar = Tripp, Dipp) and a bismuth (III)
amide. Addition of Bi[N(SiMe3)2]3 to a DME solution of
Tripp2SnH2 led to a color change from initially colorless to
shortly red eventually fading to reddish brown within a few
minutes. As initially a propellane-type structure, Bi2Sn3Tripp6
Owing to potential applications in nano- and materials
chemistry, the last few decades have seen tremendous progress
in the field of main group element cluster chemistry. Yet, the
number of examples and structural variety for this compound
class is strongly dependent on the group number. In contrast to
gallium and aluminum clusters and besides phosphorus and
germanium, polyhedral compounds of heavier group 14 and 15
elements are still rare despite the advances in the last years,1-3
let alone the examples of polyhedral mixed element
compounds.4-8 Apart from a limited number of examples of
polyhedral tin/phosphorus compounds,9-13 examples of more
metallic arsenic, antimony and bismuth homologues are even
rarer.14-17 As homo- as well as heteroelement bond formation in
these cases is still limited to just a few strategies including
stoichiometric fusion of respective elements, derivatization of
Zintl ions and reductive salt elimination, these heavier
representatives are dominated by anionic Zintl ion-type
structures.18-21 In the case of Bi/Sn systems thus far overall only
the structures of nine polyanions have been crystallographically
characterized including also trimetallic systems,22-30 while a
series of neutral, unsubstituted Sn/Bi clusters were studied in
the gas phase.31,32 We currently investigate metathesis
reactions between organotin hydrides and main group element
was
targeted,
a
stoichiometric
ratio
of
3:2
(Tripp2SnH2:Bi[N(SiMe3)2]3) was applied. Respective, purely tin
containing [1.1.1]propellanes were accessed from organotin
hydrides and tin (II) amides subjected to similar reaction
conditions in as yet unpublished results. Slow solvent
evaporation from these reactions led to crystallization of
brownish red rods suitable for X-ray crystallography after
6 days. Single crystal X-ray diffraction revealed the formation of
the mixed tin/bismuth cage Bi8Sn3Tripp6 (1, 13% yield referred
to Tripp2SnH2, 53% yield referred to Bi[N(SiMe3)2]3).
1
constitutes the first uncharged, polyhedral bismuth/tin
compound. Storage of the supernatant solutions at -30°C gave
greenish yellow crystals of cyclo-(Tripp2Sn)3 (2)36,37 as the main
byproduct next to H-N(SiMe3)2 identified by NMR spectroscopy
of reaction solutions.
isolated after 6 days
isolated after 48h
H
Ar2
Sn
Bi
Ar2 Sn
SnAr2
Ar2SnH2
+
Bi[N(SiMe3)2]3
Bi
Bi
Bi
Bi
DME
- HN(SiMe3)2
DME
- HN(SiMe3)2
SnAr2
H
Bi
Bi
Bi
Ar2 Sn
Bi Bi
3: Ar=Tripp; 6: Ar=Dipp
Ar2Sn
SnAr2
Bi Bi
Bi[N(SiMe3)2]3
Ar2SnH2
+
1: Ar=Tripp; 4: Ar=Dipp
- HN(SiMe3)2
+
cyclo-(Ar2Sn)3
2: Ar=Tripp; 5: Ar=Dipp
+
a. Institute of Inorganic Chemistry. Graz University of Technology. Stremayrgasse 9,
7: Ar6Sn4Bi2 isolated
for Ar=Dipp only
8010 Graz (Austria).
b. E-mail: roland.fischer@tugraz.at
Scheme 1 Synthesis of Bi8Sn3Ar6 (Ar = Tripp (1), Dipp (4)) from Ar2SnH2 and Bi[N(SiMe3)2]3
† Electronic Supplementary Information (ESI) available. CCDC numbers 2072047 –
2072052.
in DME.
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 4
COMMUNICATION
Journal Name
View Article Online
DOI: 10.1039/D1CC02538D
Bi4´
Bi3´
Sn1´
Sn2
Bi1
Bi3
Bi2
Bi4
Bi1´
Bi1
Bi4
Bi3
Bi2´
Bi2
Sn2
Sn1
Sn3
Bi7
Bi5
Sn1
Bi6
Bi8
Fig. 2 Molecular structures (50% probability) of 3 (left) and 6 (right) in the solid
state, hydrogens except Sn-H omitted.
Fig. 1 Molecular structures of of 1 (right) and 4 (left) in the solid state (50%
The core structure of 1 and 4 is related to that of Zintl ions of
type [Pn11]3- (Pn = P, As, Sb, Bi) and their uncharged derivatives
Pn11R3 (Pn = P (R = SiMe3, iPr), As (R = SiMe3)).41-44 Due to its
extraordinary polyhedral arrangement, the long-known [P11]3-
has been described as ‘ufosan’-type polyhedral arrangement.
Its heaviest congener [Bi11]3- was only recently isolated.45 In
accordance with the principle of valence isoelectronicity, 1 and
4 are topologically identical to [Bi11]3- with each anionic bismuth
atom interchanged with an [Ar2Sn] unit. The arrangement of the
Bi atoms in 1 and 4 is also reminiscent of the puckered structure
of grey bismuth, where the interlayer distance (3.529 Å)
exceeds the Bi-Bi distance of 3.072 Å only by ca. 15%. In 1 and
4, anti-facing Bi4 tetrahedra are connected by Bi-Bi bonds and
Ar2Sn units. Related structural motifs have been observed for
Zintl-ion like intermetalloid clusters of p-block and d-block
elements. Yet, examples for solely mixed main group metal
clusters are scarce as outlined in a recent review.46
All Bi-Bi bond lengths in 1 and 4 (2.9399(6) to 3.0267(6) Å) fall
into the known range for Bi-Bi single bonds (Bi2Ph4:47 2.990 Å,
Bi2(C18H21N)2:48 3.0648 Å), and are somewhat shorter than in
rhombohedral bismuth (3.072 Å).49 In agreement with findings
in [Bi11]3-, average bond distances between apical bismuth
atoms (Bi1 and Bi5 in 1; Bi1 and Bi1# in 4) and equatorial atoms
(Bi2 to Bi4 and Bi6 to Bi8 in 1; Bi2, Bi3, Bi4 and equivalents # in
4) are in average longer than between two equatorial bismuth
atoms (1: 3.0264(2) vs 2.9476(6) Å; 4: 3.0047(1) vs 2.9606(4) Å;
[Bi11]3-:45 3.0179(8) vs 2.9621(1) Å). The difference in bond
length can be explained by NBO analysis of a model compound
Bi8Sn3Ph6. The calculations show a higher electron occupation
of σ* Bi-Bi bond orbitals of apical bismuth atoms (0.084 e-) than
between equatorial bismuth atoms (0.049 e-) through electron
donation from adjacent σ Bi-Bi bond orbitals as well as lone
pairs of the bismuth atoms into these antibonding orbitals.
Angles around apical Bi atoms in 1 (103.47(2) to 105.19(2)°) and
4 (102.74(8) to 105.78(2)°) deviate significantly from the
expected 90° value for dominant p character of the bonding
orbitals within 2c2e bonds, similar to the angles observed
around the tricoordinate Bi atoms in [Bi11]3- (99.58(4) to
108.26(4)°).
probability), hydrogens are omitted. For key structural parameters c. f. Table 1.
In addition, small amounts of bicyclo[2.2.0] compound
Bi4Sn4H2Tripp6 (3), were isolated from concentrated reactions
1
mixtures. (Scheme 1; Figs. 1 and 2) In H NMR analysis of 1,
broad resonances were observed at rt with even more
broadened signals at elevated temperatures (35 and 45°C),
while cooling to -10°C eventually gave well-resolved spectra
with non-equivalent signals for ortho-iPr groups of the
substituents. (see SI) 1 exhibits also a broad 119Sn{1H} NMR
resonance at -925 ppm (FWHM=1230 Hz), which lacks
comparable data in literature where only shifts for terminal
R3Sn-Bi groups are available.38-40 Attempts to increase the yield
in 1 by adjusting the stoichiometry to 3:8 failed as no product
was obtained nor detected by NMR spectroscopy, c.f. Scheme
S1 in SI.
When Tripp2SnH2 was replaced by the slightly less soluble
dihydride Dipp2SnH2, slow concentration of the solvent after
2 days gave pale brownish red rhombic crystals suitable for
X-ray crystallography which single crystal X-Ray diffraction
revealed as the bicyclo[2.2.0] compound Bi4Sn4H2Dipp6 (6) in 4%
yield. (Scheme 1; Fig. 2). Nevertheless, evidence for the
formation of the expected polyhedral Bi8Sn3Dipp6 compound 4
1
and cyclo-(Dipp2Sn)3 5 were found in H and 119Sn NMR (δ = -
946 ppm, FWHM=860 Hz) spectra. Crystals of Bi8Sn3Dipp6 (4)
suitable for X-ray crystallography were obtained after removal
of the solvent and recrystallization of crude products from
n-pentane at -30°C. (Fig. 1) Again, concomitantly formed
cyclo-(Dipp2Sn)3 (5) was isolated and structurally authenticated.
Next to the isolated main products 4 and 5, also a few
octahedral, brownish red single crystals of Bi2Sn4Dipp6 (7) were
found in crude products of the conversion of Dipp2SnH2 with
Bi[N(SiMe3)2]3. (Fig. 3) Formation of
1 and 4 from
cyclotristannanes 2 and 5 via reaction with bismuth amide was
ruled out experimentally. While keeping the original reaction
mixture at rt for extended times of 6-9 days resulted in
complete consumption of 3 and 6 and formation of 1 and 4,
attempts to obtain 1 and 4 by addition of Bi[N(SiMe3)2]3 to DME
solutions of previously isolated 3 and 6 failed with ArH as the
only tractable reaction product. Only when both, Ar2SnH2 and
Bi[N(SiMe3)2]3 were added, consumption of 3 and 6 and
formation of 1 and 4 was observed. We hence believe that the
formation of labile Bi-H species are crucial steps in Bi-Bi bond
formation en route to 1 and 4, where Ar2SnH2 acts as the
reducing agent for the Bi(0) while being converted into the
cyclotristannanes 2 and 5.
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 4
ChemComm
Please do not adjust margins
Journal Name
COMMUNICATION
contribute to calculated canonical orbitals except fVoierwthAreticHleOOMnlinOe
DOI: 10.1039/D1CC02538D
and LUMO. (see SI) Energies for calculated HOMOs of Bi8Sn3Ph6
(-5.47 eV), Bi4Sn4Ph8 (-5.57 eV) and Bi2Sn4Ph6 (-5.36 eV)
coincide with each other and are largely composed of s-electron
Table 1 Bond distances and angles (Bia: apical Bi atoms, Bie: equatorial Bi atoms, for 1, 4
and 7 c.f. Figure 1 to 3).
Distances [Å] and Angles [°]
3-
1
[Bi11]
The angles around the tin atoms in 1 and 4 are widened (1:
105.58(2) to 107.64°; 4: 106.48 to 107.41(2)°) as compared to
the respective Bi-Bi--Bi angles in [Bi11]3- (94.09(5) to 96.47(4)°).
Average Bi-Sn bond distances of Bi8Sn3Ar6 (1: 2.9162(1) Å, 4:
2.9060(6) Å) agree with the average Bi-Sn bond value found in
Fig. 3 Molecular structure of 7 in the solid state (50% probability), hydrogens are
omitted. For key structural parameters c.f. Table 1.
Bia-Bie: 3.0075(7)-3.0276(6)
Bie-Bie: 2.9399(6)-2.9559(6)
Bie-Sn: 2.9027(9)-2.9433(9)
Bie-Bia-Bie: 103.47(2)-105.19(2)
Bia-Bie-Bie: 103.93(7)-104.90(2)
Bie-Sn-Bie: 105.58(2)-107.94(3)
Sn-Bie-Bia/e: 99.97(2)-98.60(2)
Bia-Bie: 2.996(1)-3.014(2)
Bie-Bie: 2.917(2)-2.998(2)
Bie-Bia-Bie:100.99(4)-104.69(4)
Bia-Bie-Bie: 99.58(4)-108.26(4)
Bia/e-Bi--Bia/e: 94.09(11)-96.47(4)
4
7
the thus far only other structurally characterized, uncharged
Bia-Bie: 2.9951(5)-3.0138(5)
Bie-Bie: 2.9553(7)-2.9714(8)
Bie-Sn: 2.8966(6)-2.9166(7)
Bie-Bia-Bie:102.74(8)-105.17(2)
Bia-Bie-Bie: 103.85(2)-105.78(2)
Bie-Sn-Bie: 106.48(2)-107.41(2)
Sn-Bie-Bia/e: 89.05(2)-99.14(2)
Bi1-Bi2: 4.084(3)
Sn-Bi: 2.909(1)-2.969(1)
Sn2-Sn4: 3.360(1)
Sn2-Bi1/2-Sn4: 69.13(3)/69.42(3)
Bi1-Sn2/4-Bi2: 87.26(3)/87.49(3)
Sn2-Sn3-Sn4: 72.84(4)
compound containing
a
Bi-Sn bond, Bi8[Sn(SiMe3)3]6
(2.926(8) Å).40 Yet, average Bi-Sn bond distances in 1 and 4 are
shorter than in bismuth/tin containing polyhedral polyanions
(e.g. [Sn2Bi2]2-: 2.9635(7) Å; [Sn3Bi5]3-:26 2.9975(11) Å). These
average bond lengths also exceed average Bi-Sn bonds in 3
(2.9046(8) Å), 6 (2.9084(5) Å), and 7 (2.939(1) Å). Both, 3 and 6,
feature a unique bicyclo[2.2.0] motif with Bi atoms as
bridgeheads. The structure can be derived from a hypothetical
Bi4 tetrahedron upon insertion of two tin atoms and
substitution by two terminal Ar2SnH groups. (Fig. 2) Owing to
the constrained geometry, the Bi-Bi-Bi angles in 3 and 6 are
quite acute at values below 90°. Dihedral angles just below 60°
density at bismuth. LUMOs decrease in energy for the extended
compounds Bi4Sn4Ph8 (-2.17 eV) and Bi8Sn3Ph6 (-2.29 eV) as
compared to Bi2Sn4Ph6 (-1.61 eV) resulting in a decrease of
HOMO-LUMO gaps with cluster size (Bi2Sn4Ph6: 3.75 eV;
Bi4Sn4Ph8: 3.39 eV; Bi8Sn3Ph6: 3.19 eV). Owing to the spherical
shape and similar to results for [Bi11]3-, the HOMO in Bi8Sn3Ph6
represents a 3d-type superatom orbital, while HOMO-3 is 2p-
orbital like. HOMO to HOMO-10 represent Sn and Bi
contribution, while HOMO-11 to HOMO-24 are ligand centered.
Hence, the 2s-type orbital in Bi8Sn3Ph6 ranks lower in energy
and corresponds to HOMO-26 as compared to HOMO-10 in the
Zintl ion.
place the Ar2SnH-substituted Bi atoms in
3 and 6 at
intramolecular distances of only 4.028(1) and 3.840(1) Å. A
similar distance between Bi atoms of 4.084(1) Å is found in 7,
where a propellane-type structure is extended with a (Dipp2Sn)
unit, similar to the purely tin containing compound Sn6Tripp6.50
While Sn-Sn bond lengths in 7 are unremarkable, Bi-Sn bonds
(avg. 2.941(2) Å) are elongated compared to 1 and 4 and angles
around bismuth in 7 are acute (69.15(4) to 80.72(5)°). Both
trends suggest dominant p character of the bonding orbitals of
the bismuth atoms in 7 and hence high s character of the lone
In summary, we have isolated the first structurally characterized
examples of uncharged Bi/Sn clusters, Bi8Sn3Ar6 and Bi2Sn4Ar6
utilizing a hydrostannolysis-type reaction of diaryltin dihydrides
and a bismuth (III) amide highlighting the synthetic potential of
the herein employed synthetic protocol. The concept is
currently extended to the preparation of other low-coordinate
homo- and heteroatomic main group element compounds.
These results will be reported elsewhere.
pairs. The small amount of isolated
7 prevented full
spectroscopic characterization thus far. Structural data of the
isolated mixed bismuth/tin compounds is summarized in the SI
(Table S1).
To obtain deeper insight into nature of bonding within the
isolated compounds (1 to 7), DFT calculations with Gaussian09
program package51 were performed for phenyl substituted
derivatives, Bi8Sn3Ph6, Bi4Sn4Ph8 and Bi2Sn4Ph6, where
calculated structures reproduce experimental data. (For full
computational details, additional canonical orbitals and
structural comparison see SI). In all cases, frontier MOs are
delocalized over several atoms or the entire metal scaffold as
expected for cluster type compounds, c.f. Fig. 4. While valence
MOs for Bi8Sn3Ph6 (LUMO+3 to HOMO-10) and Bi4Sn4Ph8
(LUMO+3 to HOMO-2) show only minor to no contribution of
the aryl ligands, substituents in Bi2Sn4Ph6 significantly
Fig. 4 Lowest unoccupied (left) and highest occupied (right) molecular orbitals of model
compounds Bi8Sn3Ph6. For full computational details and molecular orbitals of
Bi4Sn4H2Ph8 and Bi2Sn4Ph6 see SI.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 4
COMMUNICATION
Journal Name
B.G.S. thanks the Austrian Academy of Sciences for supporting 23 F. Lips and S. Dehnen, Angew. Chem. Int. Ed., 2009, 48, 6435–
View Article Online
DOI: 10.1039/D1CC02538D
this work with the DOC fellowship. We thank Dr. David J. Liptrot
for helpful discussion on this project.
6438.
24 F. Lips, M. Raupach, W. Massa and S. Dehnen, Z. anorg. allg.
Chem., 2011, 637, 859–863.
25 U. Friedrich, M. Neumeier, C. Koch and N. Korber, Chem.
Commun., 2012, 48, 10544–10546.
Conflicts of Interest
26 U. Friedrich and N. Korber, ChemistryOpen, 2016, 5, 306–310.
27 K. Mayer, J. V. Dums, W. Klein and T. F. Fässler, Angew. Chem.
Int. Ed., 2017, 56, 15159–15163.
There are no conflicts to declare.
28 F. Lips, M. Hołyńska, R. Clérac, U. Linne, I. Schellenberg, R.
Pöttgen, F. Weigend and S. Dehnen, J. Am. Chem. Soc., 2012, 134,
1181–1191.
29 M. M. Gillett-Kunnath, A. Muñoz-Castro and S. C. Sevov, Chem.
Commun., 2012, 48, 3524–3526.
30 F. Pan, L. Guggolz, F. Weigend and S. Dehnen, Angew. Chem. Int.
Ed., 2020, 59, 16638–16643.
31 S. Heiles, R. L. Johnston and R. Schäfer, J. Phys. Chem. A, 2012,
116, 7756−7764.
32 S. Heiles, K. Hofmann,R. L. Johnston and R. Schäfer,
ChemPlusChem, 2012, 77, 532–535.
33 P. R. Sharp and M. T. Rankin, Inorg. Chem., 1986, 25, 1508-1510.
34 E. Subashi, A. L. Rheingold and C. S. Weinert, Organometallics,
2006, 25, 3211–3219.
35 S. Harrypersad and D. Foucher, Chem. Commun., 2015, 51, 7120–
7123.
36 S. Masamune and L. R. Sita, J. Am. Chem. Soc., 1985, 107, 6390–
6391.
37 F. J. Brady, C. J. Cardin, D. J. Cardin, M. A. Convery, M. M.
Devereux and G. A. Lawless, J. Organomet. Chem., 1991, 421,
199–203.
38 H. Schumann and M. Schmidt, Angew. Chem., 1964, 76, 344.
39 G. Becker and M. Rößler, Z. Naturforsch., 1982, 37b, 91–96.
40 G. Linti and W. Köstler, Z. anorg. allg. Chem., 2002, 628, 63–66.
41 W. Wichelhaus and H. G. Von Schnering, Naturwissenschaften,
1973, 60, 104.
42 H. G. Schnering, D. Fenske, W. Hönle, M. Binnewies and K. Peters,
Angew. Chem. Int. Ed., 1979, 18, 679–680.
43 K.-F. Tebbe, Z. anorg. allg. Chem., 1989, 572, 115–125.
44 T. Hanauer and N. Korber, Z. anorg. allg. Chem., 2006, 632, 1135–
1140.
45 B. Weinert, A. R. Eulenstein, R. Ababei and S. Dehnen, Angew.
Chem. Int. Ed., 2014, 53, 4704–4708.
46 R. J. Wilson, N. Lichtenberger, B. Weinert and S. Dehnen, Chem.
Rev., 2019, 119, 8506–8554.
47 F. Calderazzo, A. Morvillo, G. Pelizzi and R. Poli, Chem. Commun.,
1983, 507–508.
48 S. Shimada, J. Maruyama, Y. K. Choe and T. Yamashita, Chem.
Commun., 2009, 54, 6168–6170.
Notes and references
1
2
A. Schnepf, Chem. Soc. Rev., 2007, 36, 745–758.
A. Schnepf, in Structure and Bonding, ed. S. Dehnen, Springer,
2017, vol. 119, pp. 135–200.
3
I. Krossing, in Molecular Clusters of the Main Group Elements,
eds. M. Driess and H. Nöth, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim, 2005, pp. 209–229.
4
5
6
7
8
9
A. F. Richards, H. Hope and P. P. Power, Angew. Chem. Int. Ed.,
2003, 42, 4071–4074.
A. F. Richards, M. Brynda and P. P. Power, Organometallics, 2004,
23, 4009–4011.
D. Nied, P. Ona-Burgos, W. Klopper and F. Breher,
Organometallics, 2011, 30, 1419–1428.
A. Jana, V. Huch, M. Repisky, R. J. F. Berger and D. Scheschkewitz,
Angew. Chem. Int. Ed., 2014, 53, 3514–3518.
R. J. Wilson and S. Dehnen, Angew. Chem. Int. Ed., 2017, 56,
3098–3102.
M. Dräger and B. Mathiasch, Angew. Chem., 1981, 93, 1079–
1080.
10 M. Driess, S. Martin, K. Merz, V. Pintchouk, H. Pritzkow, H.
Grützmacher and M. Kaupp, Angew. Chem. Int. Ed., 1997, 36,
1894–1896.
11 M. Westerhausen, M. Krofta, N. Wiberg, J. Knizek, H. Nöth and A.
Pfitzner, Z. Naturforsch., 1998, 53b, 1489–1493.
12 F. García, J. P. Hehn, R. A. Kowenicki, M. McPartlin, C. M. Pask, A.
Rothenberger, M. L. Stead and D. S. Wright, Organometallics,
2006, 25, 3275–3281.
13 S. Almstätter, M. Eberl, G. Balázs, M. Bodensteiner and M.
Scheer, Z. anorg. allg. Chem., 2012, 638, 1739–1745.
14 R. C. Haushalter, B. W. Eichhorn, A. L. Rheingold and S. J. Geib,
Chem. Commun., 1988, 34, 1027–1028.
15 S. Traut and C. Von Hänisch, Z. anorg. allg. Chem., 2011, 637,
1777–1783.
16 C. M. Knapp, J. S. Large, N. H. Rees and J. M. Goicoechea, Dalton
Trans., 2011, 40, 735–745.
17 A. Hinz and J. M. Goicoechea, Dalton Trans., 2018, 47, 8879–
8883.
18 R. J. Wilson, B. Weinert and S. Dehnen, Dalton Trans., 2018, 47,
14861–14869.
19 F. Lips, I. Schellenberg, R. Pöttgen and S. Dehnen, Chem. - A Eur.
J., 2009, 15, 12968–12973.
49 A. F. Holleman, N. E. Wiberg and G. Fischer, Lehrbuch der
Anorganischen Chemie, Walter de Gruyter, Berlin • New York,
2007.
20 M. M. Gillett-Kunnath, A. G. Oliver and S. C. Sevov, J. Am. Chem.
Soc., 2011, 133, 6560–6562.
21 R. J. Wilson, F. Weigend and S. Dehnen, Angew. Chem. Int. Ed.,
2020, 59, 14251–14255.
22 S. C. Critchlow and J. D. Corbett, Inorg. Chem., 1982, 21, 3286–
3290.
50 C. P. Sindlinger and L. Wesemann, Chem. Sci., 2014, 5, 2739–
2746.
51 M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al., Gaussian 09,
(Revision D.01), Gaussian, Inc., Wallingford, CT, 2013.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins