Synthesis and Crystal Structures of [W(3,6‐dichloro‐1,2‐benzenedithiolate)3]n– (n = 1, 2) and [Mo(3,6‐dichloro‐1,2‐benzenedithiolate)3]2–: Dependence of the Coordination Geometry on the Oxidation Number and Counter‐Cation in Trigonal‐Prismatic and Octahedral Structures

Abstract

AbstractThe novel complexes (Et4N)2[W(bdtCl2)3] (1a), (Ph4P)2[W(bdtCl2)3] (1b), (Et4N)[W(bdtCl2)3] (2a), (Ph4P)[W(bdtCl2)3](2b), (C5NH6)[W(bdtCl2)3] (2c), and (Et3NH)2[Mo(bdtCl2)3] (3a) (bdtCl2 = 3,6‐dichloro‐1,2‐benzenedithiolate) were prepared and characterized by X‐ray crystallographic, UV/Vis spectroscopic, and electrochemical methods. Versatile geometrical changes around the tungsten centers were observed. The trigonal‐prismatic structure of the tungsten center in (Et4N)2[W(bdtCl2)3] (1a) is changed to an intermediate structure between trigonal prismatic and octahedral upon solid‐state oxidation of the complex to (Et4N)[W(bdtCl2)3] (2a). Replacement of the counter‐cation of (Et4N)2[W(bdtCl2)3] (1a) with Ph4P+ also resulted in geometrical changes and somewhat of an octahedral contribution is included in (Ph4P)2[W(bdtCl2)3] (1b). However, almost the same coordination structures are present in the series of structures (Et4N)[W(bdtCl2)3] (2a), (Ph4P)[W(bdtCl2)3] (2b), and (C5NH6)[W(bdtCl2)3] (2c), with an oxidation number of +5. These structures adopt an intermediate geometry between trigonal prismatic and octahedral. No geometrical change was observed upon changing the metal center from tungsten to molybdenum in [M(bdtCl2)3]2– (M = W and Mo). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)