Chemistry of 2-thienyl derivatives of arsenic and antimony: Synthesis and characterization; X-ray structure of [PdCl2{(C4H3S)3As}2]

Abstract

Tri-(2-thienyl)-arsine and -stibine, Th3E (E =As; Sb), were prepared by the reaction of 2-thienylmagnesium bromide and the appropriate metal trichloride. Several derivatives of the general formulae E(C4H3S)3X2 (X = Cl, Br, OAc; E = As, Sb) have been prepared. So as to explore the coordination behaviour of Th3E, a series of complexes of the type MCl2(AsTh3)2, [PdX2(μ-Y)2(AsTh3)2], [PdCl(S∧S)(AsTh3)] [M = Pd, Pt; X = Cl, Me; Y = Cl, dmpz, pz, S∧S = S2P(OEt)2, S2P(OPri)2] have also been prepared. All complexes have been characterized by elemental analysis, IR and NMR spectroscopy, and show that these ligands coordinate to palladium(II) and platinum(II) through E (As or Sb) exclusively. The molecular structure of [PdCl2(AsTh3)2] has been established by X-ray structural analysis and reveals a square planar geometry for palladium defined by an As2Cl2 donor set. © 2002 Elsevier Science Ltd. All rights reserved.