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Dalton Transactions
Page 6 of 7
ARTICLE
Journal Name
chains along the a-axis with alternating 5e and 9e molecules in readily undergoes a C-C coupling process, presVuiemwaAbrtlicyle Obnylinae
DOI: 10.1039/C6DT00229C
the solid state.
radical mechanism.
Acknowledgements
We are indebted to Dr. Dirk Michalik for NMR measurements.
Notes and references
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Figure 7. ORTEP drawing of the molecular structure of 11g (left) and 11f (right).
Thermal ellipsoids with 50% probability at 173 K (hydrogen atoms omitted for clarity).
Selected distances (Å) and angles (°): 11g: Bi1-N1 2.129(2), Bi1-N1' 2.147(2), Bi1-N2
2.165(2), N1-Bi1-N2 95.29(8), N2-Bi1-N1' 96.61(8), N1'-Bi1-N1 75.62(8), Bi1-N1-C1
127.0(2), C1-N1-Bi1' 127.3(2), Bi1'-N1-Bi1 104.38(8), Bi1-N1-C1-C2 155.7(2); 11f: Bi1-N1
2.16(1), Bi1-N2 2.164(7), Bi1-N3 2.176(9), N2-Bi2 2.154(9), Bi2-N1 2.142(7), Bi2-N4
2.175(9), N1-Bi1-N2 77.1(3), N2-Bi1-N3 99.5(3), N3-Bi1-N1 101.7(3), N1-Bi2-N2 77.7(3),
N2-Bi2-N4 102.1(3), N4-Bi2-N1 98.7(3), Bi1-N2-C20 127.9(7), C20-N2-Bi2 129.7(6), Bi2-
N2-Bi1 102.3(4), Bi1-N2-C20-C21 142.6(8).
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Conclusions
Depending on the steric demand of the aryl group and the
used stoichiometry the reaction of RN(SiMe3)Li with BiCl3 leads
to mono, double or even triple substitution at the bismuth
atom. With bulky groups attached to the amide, preferentially
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10
11
12
13
14
15
16
17
the products of mono substitution (
while triple substitution is mainly observed for smaller groups.
The aminodichlorobismuthanes with smaller R groups readily
undergo BiCl3 elimination reactions to form diaminochlorobis-
muthanes ( ) or even triaminobismuthanes (12). Instead of
5) are found (Scheme 3),
5
9
triaminobismuthanes also cyclo-dibismadiazanes 11 can be
formed when an excess of amide with a less bulky group is
used and in solution both compounds 11 and 12 can even co-
exist as well as in the solid state. For bulky groups, which are
not able to form triple substitution products, the reaction of a
huge excess of amide with BiCl3 leads to the formation of the
amine RN(SiMe3)H. We want to stress that all reaction
conditions (stoichiometry, solvent, reaction temperature, the
use of isolated lithium amide or in situ generated and use of
sublimed or unsublimed BiCl3) have a strong influence on the
formed products and their distribution in mixtures. Even small
changes to the reaction conditions can lead to very different
results.
In the solid state the Lewis acidic bismuth atoms in these
compounds can be stabilized by secondary interactions with
aromatic solvents or intramolecularly, such as in the terphenyl
substituted species. Another way to stabilize bismuth centers
was established by bridging Cl atoms as found in some of the
mono- and dichloro bismuthanes.
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20
21
22
23
C-C coupling reactions rather than substitution was only
observed for the supermesityl substituted derivative, which
forms in the first step the mono-substitution product, that
W. Clegg, N. A. Compton, R. J. Errington, G. A. Fisher, M. E.
Green, D. C. A. Hockless and N. C. Norman, Inorg. Chem.,
1991, 30, 4680–4683.
6 | J. Name., 2012, 00, 1-3
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