Vanadium(IV) thiolate chemistry: preparation, structure, and properties of [VE(SCH2CH2S)2]2- (E = O,S)
Vanadium(IV) thiolate chemistry: preparation, structure, and properties of [VE(SCH2CH2S)2]2- (E = O,S)
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硫醇钒(IV)化学：[VE(SCH2CH2S)2]2- (E = O,S) 的制备、结构和性质
DOI：
10.1021/ic00214a040
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发表时间：
1985
影响因子：
4.6
通讯作者：
G. Christou
中科院分区：
文献类型：
--
作者：
J. K. Money;J. Huffman;G. Christou
报道了钒(IV)与乙烷-1，2-二硫代硫酸酯配体(EDT/SUP2-/)配合物的合成、结构和性质。(nme/sub4/)Na(VO(Edt)/sub2/)x2EtOH属单斜晶系P2/sub1//n空间群，晶胞参数为a=21.312(5)A，b=10.906(2)A，c=9.381(1)A，.=92.77(1)/sup 0/，Z=4。钒的配位构型为方锥配位，顶端为多键氧(V-O=1.625(2)A)，碱基为四个硫原子。阴离子、阳离子和溶剂分子堆积成C/sub2H/对称性的离散单元。(Vo(Edt)/sub2/)/sup 2-/与六甲基二硅烷干净利落地转化为(vs(Edt)/sub2/)/sup-/，(Me/sub3/Si)/sub2/S(PPh/sub4/)Na(vs(Edt)/sub2/)xxEt/sub2/O结晶在三斜空间群P1中，晶胞参数为(约-160/sup 0/C)a=17.201(5)A，b=10.983(3)A，C=9.919(3)A，..阿尔法帽..=65.84(1)/sup 0/，..beta.=106.63(1)/超级0/..伽马..=93.32(2)/sup_2/，Z=2。除顶硫(V-S=2.087(1)A)外，阴离子与(VO(Edt)/SUB_2/)/sup_2~-同构型。阴离子、更多的阳离子和溶剂分子再次填充到离散的二聚体中，但具有不同的D/亚2小时/对称性结构。这只是含有V=S/超级2+/部分的结构特征物种的第二个例子。对这两种配合物进行了红外、电化学和紫外可见光谱研究。参考文献32篇，附图4幅，表格4张。
The synthesis, structure, and properties of vanadium(IV) complexes with the ethane-1,2-dithiolate ligand (edt/sup 2 -/) are described. (NMe/sub 4/)Na(VO(edt)/sub 2/) x 2EtOH crystallizes in monoclinic space group P2/sub 1//n with unit cell parameters (at ca. -159/sup 0/C) a = 21.312 (5) A, b = 10.906 (2) A, c = 9.381 (1) A, ..beta.. = 92.77 (1)/sup 0/, and Z = 4. The vanadium is in a square-pyramidal coordination geometry with the multiply bonded oxygen at the apex (V-O = 1.625 (2) A) and four ligand sulfur atoms in the base. The anion, cations, and solvent molecules pack into discrete units of C/sub 2h/ symmetry. (VO(edt)/sub 2/)/sup 2 -/ was cleanly converted into (VS(edt)/sub 2/)/sup 2/)/sup -/ with hexamethyldisilthiane, (Me/sub 3/Si)/sub 2/S. (PPh/sub 4/)Na(VS(edt)/sub 2/) x xEt/sub 2/O crystallizes in triclinic space group P1 with unit cell parameters (at ca. -160/sup 0/C) a = 17.201 (5) A, b = 10.983 (3) A, c = 9.919 (3) A, ..cap alpha.. = 65.84 (1)/sup 0/, ..beta.. = 106.63 (1)/sup 0/ ..gamma.. = 93.32 (2)/sup 0/, and Z = 2. The anion is isostructural with (VO(edt)/sub 2/)/sup 2 -/ except for the presence of the apical sulfur (V-S = 2.087 (1) A). The anion,more » cations, and solvent molecules again pack into discrete dimers, but of a different structure of D/sub 2h/ symmetry. This is only the second example of a structurally characterized species containing the V=S/sup 2 +/ moiety. Infrared, electrochemical, and UV/visible studies of the two complexes are described. 32 references, 4 figures, 4 tables.« less