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• W4285011954 endingPage "116030" @default.
• W4285011954 startingPage "116030" @default.
• W4285011954 abstract "The oxidation of coordinated phosphine of square planar Ni(II) complexes by peroxide proceeded via oxidative addition of peroxide at Ni center followed by the reductive elimination of phosphine oxide passing through an intermediate of Ni IV (OH) 2 complex. A tetranuclear Ni-complex of [(NiL) 4 ] ( 1 ) (where H 2 L = (E)-2-(((2-mercaptophenyl)imino)methyl)-6-methoxyphenol) was synthesized and fully characterized. The solvent dependent behaviour of 1 showed the existence of monomeric species which was well explained using several spectroscopic evidences. Compound [NiL(PPh 3 )] ( 2 ) and [LNi(dppe)NiL] ( 3 ) were synthesized by the reaction of 1 with respective phosphine in acetone (dppe = (Ph 2 PCH 2 CH 2 PPh 2 ). All Ni-complexes were characterized by x-ray structure analysis and other spectroscopic techniques like 1 H NMR, positive-ion ESI etc. The electrochemical responses for all Ni-complexes were explained. The reactivity of 2 and 3 with H 2 O 2 and t BuOOH were explored in homogenous solution which identified that coordinated phosphine group at Ni(II) centre was oxidized and the reaction was preceded via oxygen atom transfer (OAT) reaction. The mechanism of OAT reaction of 2 with H 2 O 2 was proposed based on the detection of the intermediates using several possible spectroscopic tools and density functional theory (DFT) calculation approaches which demonstrated the highly exothermic nature of overall reaction (ΔG sol = -85.3 Kcal mol −1 ) and the reaction pathway involved the oxidative addition of H 2 O 2 at Ni(II) center to form an intermediate Ni (IV) (OH) 2 complex ( INT1 ) followed by the reductive elimination of O = PPh 3 occurred." @default.
• W4285011954 created "2022-07-12" @default.
• W4285011954 creator A5029319949 @default.
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• W4285011954 date "2022-09-01" @default.
• W4285011954 modified "2023-09-24" @default.
• W4285011954 title "The access of {NiIV(OH)2} intermediate in Ni(II) mediated oxygen atom transfer to coordinated Phosphine: Combined experimental and computational studies" @default.
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• W4285011954 doi "https://doi.org/10.1016/j.poly.2022.116030" @default.
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