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Issue 26, 2012
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Substituent effects on Ni–S bond dissociation energies and kinetic stability of nickel arylthiolate complexes supported by a bis(phosphinite)-based pincer ligand

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Abstract

Pincer complexes of the type [2,6-(R2PO)2C6H3]NiSC6H4Z (R = Ph and i-Pr; Z = p-OCH3, p-CH3, H, p-Cl, and p-CF3) have been synthesized from [2,6-(R2PO)2C6H3]NiCl and sodium arylthiolate. X-ray structure determinations of these thiolate complexes have shown a somewhat constant Ni–S bond length (approx. 2.20 Å) 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)2C6H3]Ni” rather than “[2,6-(i-Pr2PO)2C6H3]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.

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

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Supplementary files

Article information


Submitted
21 Feb 2012
Accepted
29 Mar 2012
First published
30 Mar 2012

Dalton Trans., 2012,41, 7959-7968
Article type
Paper

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

J. Zhang, A. Adhikary, K. M. King, J. A. Krause and H. Guan, Dalton Trans., 2012, 41, 7959
DOI: 10.1039/C2DT30407D

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