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
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[W(3,6-二氯-1,2-苯二硫醇)3]n- (n = 1, 2) 和 [Mo(3,6-二氯-1,2-苯二硫醇)3]2 的合成和晶体结构–：三棱柱和八面体结构中配位几何对氧化数和反阳离子的依赖性
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发表时间：
2005
期刊：
影响因子：
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通讯作者：
H. Tsukube
中科院分区：
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作者：
H. Sugimoto;Yuuki Furukawa;Makoto Tarumizu;H. Miyake;Koji Tanaka;H. Tsukube
新的配合物(Et4N)2[W(BdtCl2)3](La)，(Ph4P)2-[W(BdtCl2)3](1b)，(Et4N)[W(BdtCl2)3](2a)，(Ph4P)[W(BdtCl2)3](2b)，(C5NH6)[W(BdtCl2)3](2c)，合成了(Et3NH)2[Mo(BdtCl2)3](3a)(bdtCl2=3，6-二氯-1，2-苯二硫酸酯)，并用X-射线单晶衍射、UV/Vis光谱和电化学方法对其结构进行了表征。观察到钨中心周围的各种几何变化。(Et4N)2[W(BdtCl2)3](1a)固相氧化成(Et4N)[W(BdtCl2)3](2a)后，钨中心的三棱柱结构转变为介于三棱柱和八面体之间的中间结构。用Ph_4P+取代(Et_4N)_2[W(BdtCl2)_3](La)的反阳离子也引起了几何构型的变化，并且在(Ph_4P)_2-[W(BdtCl2)_3](1b)中有一定的八面体贡献。然而，(Et4N)[W(BdtCl2)3](2a)，(Ph4P)[W(BdtCl2)3](2b)和(C5NH6)[W(BdtCl2)3](2c)系列结构中存在几乎相同的配位结构，氧化数为+5。这些结构采用介于三角和八面体之间的中间几何构型。在[M(BdtCl2)3]2-(M=W和Mo)中，金属中心由钨变为钼时，没有观察到几何形状的变化。
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).