钌（II）硫醇和 H2S 配合物的合成、表征和热力学性质。

Ruthenium(II) thiol and H2S complexes: synthesis, characterization, and thermodynamic properties.

机构信息

Department of Chemistry, University of British Columbia, Vancouver, British Columbia V6T 1Z1, Canada.

出版信息

Inorg Chem. 2012 May 7;51(9):5427-34. doi: 10.1021/ic3004118. Epub 2012 Apr 11.

Abstract

The known, green, five-coordinate species trans-RuCl(2)(P-N)(PPh(3)) react with R'SH thiols to give yellow cis-RuCl(2)(P-N)(PPh(3))(R'SH) products (P-N = o-diphenylphosphino-N,N'-dimethylaniline; R' = alkyl). The MeSH and EtSH compounds are structurally characterized, with the former being the first reported for a transition metal-MeSH complex, while the thiol complexes with R' = (n)Pr, (i)Pr, (n)Pn (pentyl), (n)Hx (hexyl), and Bn (benzyl) are synthesized in situ. Other trans-RuX(2)(P-N)(PR(3)) complexes (X = Br, I; R = Ph, p-tolyl) are synthesized, and their H(2)S adducts, of a type reported earlier by our group, are also prepared. Thermodynamic data are presented for the reversible formation of the MeSH and EtSH complexes and the H(2)S analogues. The Ru(II)Cl(2)(P-N)(PPh(3)) complex in solution decomposes under O(2) to form Ru(III)Cl(P-N)(μ-O)(μ-Cl)(2).

摘要

已知的绿色五配位物种反式 RuCl(2)(P-N)(PPh(3))与 R'SH 硫醇反应生成黄色顺式 RuCl(2)(P-N)(PPh(3))(R'SH)产物（P-N =邻-二苯基膦基-N,N'-二甲苯胺；R' = 烷基）。MeSH 和 EtSH 化合物的结构得到了表征，前者是第一个报道的过渡金属-MeSH 配合物，而具有 R' = (n)Pr、(i)Pr、(n)Pn（戊基）、(n)Hx（己基）和 Bn（苄基）的硫醇配合物则是原位合成的。还合成了其他的反式 RuX(2)(P-N)(PR(3))配合物（X = Br，I；R = Ph，p-甲苯基），并制备了我们小组先前报道的其 H(2)S 加合物。还提出了可逆形成 MeSH 和 EtSH 配合物以及 H(2)S 类似物的热力学数据。溶液中的 Ru(II)Cl(2)(P-N)(PPh(3))配合物在 O(2)下分解，形成Ru(III)Cl(P-N)(μ-O)(μ-Cl)(2)。