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

Dalton Transactions : an International Journal of Inorganic Chemistry
Jie ZhangHairong Guan

Abstract

Pincer complexes of the type [2,6-(R(2)PO)(2)C(6)H(3)]NiSC(6)H(4)Z (R = Ph and i-Pr; Z = p-OCH(3), p-CH(3), H, p-Cl, and p-CF(3)) have been synthesized from [2,6-(R(2)PO)(2)C(6)H(3)]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-(Ph(2)PO)(2)C(6)H(3)]Ni" rather than "[2,6-(i-Pr(2)PO)(2)C(6)H(3)]Ni", and bonds least favourably with hydrogen. The reactions of the thiolate complexes with halogenated compounds such as PhCH(2)Br, CH(3)I, CCl(4), and Ph(3)CCl have been examined and several mechanistic pathways have been explored.

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Citations

Nov 6, 2012·Acta Crystallographica. Section E, Structure Reports Online·Man-Lung KwanRichard E Sykora
Dec 17, 2014·Inorganic Chemistry·Tapash Deb, Michael P Jensen
Mar 18, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Ting LiuXuenian Chen
Mar 17, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Gleason L O WilsonHairong Guan
Nov 27, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Sathiyamoorthy Murugesan, Karl Kirchner
Feb 16, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Jie ZhangXuenian Chen
Sep 3, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Bula CaoXuenian Chen
Oct 18, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Sandeep Kaur-GhumaanTorsten Beweries
Apr 15, 2021·Inorganic Chemistry·Lauren L CordeiroCharles G Riordan

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