论文信息 - 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

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

The novel complexes (Et 4 N) 2 [W(bdtCl 2 ) 3 ] (la), (Ph 4 P) 2 -[W(bdtCl 2 ) 3 ] (1b), (Et 4 N)[W(bdtCl 2 ) 3 ] (2a), (Ph 4 P)[W(bdtCl 2 ) 3 ] (2b), (C 5 NH 6 )[W(bdtCl 2 ) 3 ] (2c), and (Et3NH)2[Mo(bdtCl2)3] (3a) (bdtCl 2 = 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 (Et 4 N ) 2[W(bdtCl 2 ) 3 ] (la) is changed to an intermediate structure between trigonal prismatic and octahedral upon solid-state oxidation of the complex to (Et 4 N)[W(bdtCl 2 ) 3 ] (2a). Replacement of the counter-cation of (Et 4 N) 2 [W(bdtCl 2 ) 3 ] (la) with Ph 4 P + also resulted in geometrical changes and somewhat of an octahedral contribution is included in (Ph 4 P) 2 -[W(bdtCl 2 ) 3 ] (1b). However, almost the same coordination structures are present in the series of structures (Et 4 N)[W(bdtCl 2 ) 3 ] (2a), (Ph 4 P)[W(bdtCl 2 ) 3 ] (2b), and (C 5 NH 6 )[W(bdtCl 2 ) 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(bdtCl 2 ) 3 ] 2 - (M = W and Mo).

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