COORDINATION CHEMISTRY OF STERICALLY HINDERED THIOLATE LIGANDS - PREPARATION AND STRUCTURAL CHARACTERIZATION OF THE OLIGOMERIC HOMOLEPTIC COMPLEXES [CU(SC6H4-ORTHO-SIME3)]12 AND [(AG(SC6H4-ORTHO-SIME3))4]2 AND A COMPARISON TO THE STRUCTURE OF THE MONONUCLEAR SPECIES (ET4N)2[CD(SC6H4-ORTHO-SIME3)4]
COORDINATION CHEMISTRY OF STERICALLY HINDERED THIOLATE LIGANDS - PREPARATION AND STRUCTURAL CHARACTERIZATION OF THE OLIGOMERIC HOMOLEPTIC COMPLEXES [CU(SC6H4-ORTHO-SIME3)]12 AND [(AG(SC6H4-ORTHO-SIME3))4]2 AND A COMPARISON TO THE STRUCTURE OF THE MONONUCLEAR SPECIES (ET4N)2[CD(SC6H4-ORTHO-SIME3)4]
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DOI：
10.1021/ic00306a013
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发表时间：
1989-04-05
影响因子：
4.6
通讯作者：
ZUBIETA, J
中科院分区：
文献类型：
--
作者：
BLOCK, E;GERNON, M;ZUBIETA, J
引言金属硫醇盐配位化学是基本的化学兴趣，鉴于结构的多样性和相关的金属网站的各种氧化还原活性金属蛋白。此外，在金属配合物中，RS”基团可与硫代配体S2”相比较，其优点是取代基R可被操纵以实现连接能力的空间和电子控制，并设计金属位点周围的环境，从而提供小底物分子可接近的金属硫醇盐位点。作为我们对新型空间位阻硫醇盐配体的化学的持续研究的一部分，我们制备了硫醇1和2（方案I和2）。8· 9甲硅烷基化的硫醇作为具有“可调”空间需求的一类新的受阻配体的代表是令人感兴趣的。甲硅烷基取代基和甲硅烷基数目的变化应导致配体的空间锥角10的相应变化。此外，2-（三有机甲硅烷基）苯硫酚1和2，6-双（三有机甲硅烷基）苯硫酚可以提供杯芳烃样环状聚苯硫酚的合成前体，其能够紧密地容纳金属，同时提供小线性分子可接近的空腔。本文报道了2-（三甲基硅基）苯硫酚与Ib族金属Cd、Cu和Ag的配位性质。这一选择部分是由Cu+、Ag+和Cd 2+与空间上无害的硫醇盐形成聚合物或低聚物的有据可查的倾向决定的（1）（a）Dance，IG Polyhedron 1986，J，1037。(b)Blower，P.G.; Dilworth，J. R.协调1987，76，121.
Introduction Metal-thiolate coordinationchemistry is of fundamental chemical interest in view of the structural diversity displayed and the relevance to the metal sites of a variety of redox-active me-talloproteins. 1 Furthermore, in metal complexes, the RS" group can be compared with the sulfido ligand S2", with the advantage that the substituent R can be manipulated to effect steric and electronic controlof ligating ability and to engineer the envi-ronment about the metal site, thus affording metal-thiolate sites accessible to small substrate molecules. As part of our continuing investigations of the chemistry of novel sterically hindered thiolate ligands, 2" 7 we have prepared the thiols 1 and 2 (Schemes I and). 8· 9 The silylated thiols are of interest as representatives of a new class of hindered ligands with “tunable” steric demand. Variation in both the silyl substituent and the number of silyl groups should lead to a corresponding variation in the steric cone angle10 of the ligand. Furthermore, the 2-(triorganosilyl) thiophenols 1 and 2, 6-bis (triorganosilyl) thiophenols may provide synthetic precursors for calixarene-like11 cyclic po-lythiophenols capable of snugly accommodating a metal while providing a cavity accessible to smalllinear molecules. In this paper, we report the coordinating properties of 2-(tri-methylsilyl) thiophenol with the group lib metal Cd and the group lb metals Cu and Ag. This choice was dictated in part by the well-documented propensity of Cu+, Ag+, and Cd2+ to form polymeric or oligomeric species with sterically innocent thiolate (1)(a) Dance, IG Polyhedron 1986, J, 1037.(b) Blower, P. G.; Dilworth, J. R. Coord. Chem. Rev. 1987, 76,121.