Substituent effects on Ni-S bond dissociation energies and kinetic stability of nickel arylthiolate complexes supported by a bis(phosphinite)-based pincer ligand

被引：40

作者：

Zhang, Jie ^{[1
]}

Adhikary, Anubendu ^{[1
]}

King, Krista M. ^{[1
]}

Krause, Jeanette A. ^{[1
]}

Guan, Hairong ^{[1
]}

机构：

[1] Univ Cincinnati, Dept Chem, Cincinnati, OH 45221 USA

来源：

DALTON TRANSACTIONS | 2012年 / 41卷 / 26期

基金：

美国国家科学基金会;

关键词：

DIPHOSPHINITO POCOP COMPLEXES; KHARASCH ADDITION-REACTION; SINGLE ELECTRON-TRANSFER; ZINC THIOLATE COMPLEXES; TRANSITION-METAL; MOLECULAR-STRUCTURE; SYNTHETIC ANALOGS; PROTON-TRANSFER; SPIN-RESONANCE; ARYL SULFIDES;

D O I：

10.1039/c2dt30407d

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Pincer complexes of the type [2,6-(R2PO)(2)C6H3]NiSC(6)H(4)Z (R = Ph and i-Pr; Z = p-OCH3, p-CH3, H, p-Cl, and p-CF3) have been synthesized from [2,6-(R2PO)(2)C6H3]NiCl and sodium arylthiolate. X-ray structure determinations of these thiolate complexes have shown a somewhat constant Ni-S bond length (approx. 2.20 angstrom) but an almost unpredictable orientation of the thiolate ligand. Equilibrium constants for various thiolate exchange (between a nickel thiolate complex and a free thiol, or between two different nickel thiolate complexes) reactions have been measured. Evidently, the thiolate ligand with an electron-withdrawing substituent prefers to bond with "[2,6-(Ph2PO)(2)C6H3]Ni" rather than "[2,6-(i-Pr2PO)(2)C6H3]Ni", and bonds least favourably with hydrogen. The reactions of the thiolate complexes with halogenated compounds such as PhCH2Br, CH3I, CCl4, and Ph3CCl have been examined and several mechanistic pathways have been explored.

引用

页码：7959 / 7968

页数：10

共 87 条

[1] A Dinuclear Ni(I) System Having a Diradical Ni2N2 Diamond Core Resting State: Synthetic, Structural, Spectroscopic Elucidation, and Reductive Bond Splitting Reactions [J].