Defining and Controlling the Aminoethanethiolate Chemistry of Bismuth(III): Synthesis and Comprehensive Characterization of the Homologous Thiolatobismuth Series

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• 作者：Glen G. Briand ; Neil Burford ; T. Stanley Cameron ; and Witold Kwiatkowski
• 刊名：Journal of the American Chemical Society
• 出版年：1998
• 出版时间：November 11, 1998
• 年：1998
• 卷：120
• 期：44
• 页码：11374 - 11379
• 全文大小：95K
• 年卷期：v.120,no.44(November 11, 1998)
• ISSN：1520-5126

文摘

Synthetic, spectroscopic (IR, Raman, NMR, APCI-MS), and X-ray crystallographic studiesdemonstrate that the highly favorable thiolation of bismuth can be controlled by manipulating stoichiometricconditions for the reactions of BiCl₃ or Bi(NO₃)₃ with aminoethanethiolate anions. With this approach, thefirst homologous series of mono-, bis-, and tris-thiolated bismuth complexes has been isolated and comprehensively characterized, which includes tris(aminoethanethiolato)bismuth(III) (1), bis(aminoethanethiolato)bismuth(III) nitrate (2NO₃), and bis(aminoethanethiolato)bismuth(III) chloride (2Cl), the correspondingdimethylaminoethanethiolato derivatives (1(Me) and 2(Me)Cl), and dimethylaminoethanethiolatobismuth(III)chloride (3(Me)). The acyclic dimethylammoniumethanethiolatobismuth(III) chloride (4(Me)) extends theseries and represents decoupling of the amine by protonation with retention of monothiolation. The syntheticguidelines are likely to be generally applicable to other metals and other asymmetric ligands.