- Insertion of benzyne into a Bi-S bond: A new synthetic route to ortho -functionalized bismuthanes and its application to the synthesis of dibenzothiophene
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ortho-Arylthio triarylbismuthanes [2-(Ar′S)C6H 4]nBiAr3-n have been conveniently synthesized by insertion of benzyne into the bismuth-sulfur bond of (Ar′S) nBiAr3-n (n = 1, 2). A similar insertion takes place when a homologous antimony congener is used, but no reaction is observed with its phosphorus analogue. This suggests a clear difference in the bond strength between pnictogen-sulfur bonds. The carbon-bismuth bond of [2-(2-BrC 6H4S)C6H4]nBiAr 3-n undergoes Pd-catalyzed intramolecular cross-coupling to produce dibenzothiophene in good yield. An X-ray crystallographic study of 2-(2-BrC 6H4S)C6H4BiTol2 (Tol = 4-MeC6H4) reveals that this molecule is present in a dimeric structure, where the six heteroatoms including bismuth, sulfur, and bromine are linked through the nonbonded intramolecular bismuth-sulfur and intermolecular sulfur-bromine and bromine-bromine interactions.
- Chen, Jing,Murafuji, Toshihiro,Tsunashima, Ryo
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experimental part
p. 4532 - 4538
(2011/11/13)
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- Some Group 15 Pseudo-halides and the Crystal Structure of Diphenylbismuth(III) Thiocyanate
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A crystal structure determination showed that in diphenylbismuth thiocyanate the thiocyanate group bridges between pairs of bismuth atoms to give infinite chains in which alternate bismuth atoms are co-ordinated to either two nitrogen or two sulfur atoms.The conformation of the resulting chain is a 'rectangular spiral', in contrast to the 'triangular spiral' structure of the related diphenylantimony thiocyanate.Unstable diphenylantimony selenocyanate has also been prepared and the complexity in the C-N stretching region of the IR spectrum suggests a structure similar to that of the thiocyanate analogue.Diphenylarsenic thiocyanate is a liquid at room temperature and a conventional 1,3-thiocyanate-bridged structure is suggested from IR data.
- Forster, Glynis E.,Begley, Michael J.,Sowerby, D. Bryan
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p. 383 - 388
(2007/10/02)
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- New Reagents, XXXIV. (Diphenylarsino)methyllithium: Synthesis and Preparative Applications
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(Diphenylarsino)methyl iodide (3) was synthesized for the first time (76 percent). (Diphenylarsino)methyllithium (2), stable at 20 deg C, is accessible from 3 (ca. 100 percent) by iodine-lithium exchange with butyl- or phenyllithium and by organoelement-lithium exchange with butyllithium from diphenylarsane (4d; 92 percent). 2, prepared from 4d, gives far better yields of (diphenylarsino)alkanes by the reaction with alkyl halides than 2, obtained from 3.To the contrary, no difference is observed in the reactivity of 2 from 3 or 4d towards aldehydes and ketones.
- Kauffmann, Thomas,Altepeter, Bruno,Klas, Norbert,Kriegesmann, Reinhard
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p. 2353 - 2364
(2007/10/02)
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