The reactions of the Cu(II)-nitrilotris(methylenephosphonic acid) complex with alkyl radicals in aqueous solutions

Guy Yardeni; Dan Meyerstein; Elena Mikhailovich-Jivin; Lioubov Kats; Haim Cohen; Israel Zilbermann; Eric Maimon

doi:10.1016/j.ica.2020.119759

The reactions of the Cu(II)-nitrilotris(methylenephosphonic acid) complex with alkyl radicals in aqueous solutions

Guy Yardeni, Dan Meyerstein, Elena Mikhailovich-Jivin, Lioubov Kats, Haim Cohen, Israel Zilbermann, Eric Maimon

Department of Chemical Sciences

Research output: Contribution to journal › Article › peer-review

Abstract

The reactions of the radicals [rad]R, [rad]R = [rad]CH₃ or [rad]CH₂OH, with the complex Cu^II(ntp)(H₂O) were studied. The kinetics of formation of the transient complexes (ntp)Cu^III-R fit pseudo first order rate laws. The mechanism of decomposition of the transient complex (ntp)Cu^III-CH₃ at pH ≥ 7 involves homolysis of the Cu^III-C bond. However, at pH < 6 the decomposition mechanisms of the transient complexes (ntp)Cu^III-R involve inter-molecular electron transfer to Cu^II(ntp)(H₂O) and slow intra-molecular electron transfer.

Original language	English
Article number	119759
Journal	Inorganica Chimica Acta
Volume	511
DOIs	https://doi.org/10.1016/j.ica.2020.119759
State	Published - 1 Oct 2020

Keywords

Alkyl radicals
Inter- and intra-molecular electron transfer
Ntp complexes
Pulse-radiolysis

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10.1016/j.ica.2020.119759

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title = "The reactions of the Cu(II)-nitrilotris(methylenephosphonic acid) complex with alkyl radicals in aqueous solutions",

abstract = "The reactions of the radicals [rad]R, [rad]R = [rad]CH3 or [rad]CH2OH, with the complex CuII(ntp)(H2O) were studied. The kinetics of formation of the transient complexes (ntp)CuIII-R fit pseudo first order rate laws. The mechanism of decomposition of the transient complex (ntp)CuIII-CH3 at pH ≥ 7 involves homolysis of the CuIII-C bond. However, at pH < 6 the decomposition mechanisms of the transient complexes (ntp)CuIII-R involve inter-molecular electron transfer to CuII(ntp)(H2O) and slow intra-molecular electron transfer.",

keywords = "Alkyl radicals, Inter- and intra-molecular electron transfer, Ntp complexes, Pulse-radiolysis",

author = "Guy Yardeni and Dan Meyerstein and Elena Mikhailovich-Jivin and Lioubov Kats and Haim Cohen and Israel Zilbermann and Eric Maimon",

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T1 - The reactions of the Cu(II)-nitrilotris(methylenephosphonic acid) complex with alkyl radicals in aqueous solutions

AU - Yardeni, Guy

AU - Meyerstein, Dan

AU - Mikhailovich-Jivin, Elena

AU - Kats, Lioubov

AU - Cohen, Haim

AU - Zilbermann, Israel

AU - Maimon, Eric

PY - 2020/10/1

Y1 - 2020/10/1

N2 - The reactions of the radicals [rad]R, [rad]R = [rad]CH3 or [rad]CH2OH, with the complex CuII(ntp)(H2O) were studied. The kinetics of formation of the transient complexes (ntp)CuIII-R fit pseudo first order rate laws. The mechanism of decomposition of the transient complex (ntp)CuIII-CH3 at pH ≥ 7 involves homolysis of the CuIII-C bond. However, at pH < 6 the decomposition mechanisms of the transient complexes (ntp)CuIII-R involve inter-molecular electron transfer to CuII(ntp)(H2O) and slow intra-molecular electron transfer.

AB - The reactions of the radicals [rad]R, [rad]R = [rad]CH3 or [rad]CH2OH, with the complex CuII(ntp)(H2O) were studied. The kinetics of formation of the transient complexes (ntp)CuIII-R fit pseudo first order rate laws. The mechanism of decomposition of the transient complex (ntp)CuIII-CH3 at pH ≥ 7 involves homolysis of the CuIII-C bond. However, at pH < 6 the decomposition mechanisms of the transient complexes (ntp)CuIII-R involve inter-molecular electron transfer to CuII(ntp)(H2O) and slow intra-molecular electron transfer.

KW - Alkyl radicals

KW - Inter- and intra-molecular electron transfer

KW - Ntp complexes

KW - Pulse-radiolysis

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JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

M1 - 119759

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The reactions of the Cu(II)-nitrilotris(methylenephosphonic acid) complex with alkyl radicals in aqueous solutions

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