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

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
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2020 Elsevier B.V.

Funding

This study was supported by a grant from the Israeli Atomic Energy Committee and the Planning and Budgeting committee of the Israel Council of Higher Education . This study was supported by a grant from the Israeli Atomic Energy Committee and the Planning and Budgeting committee of the Israel Council of Higher Education.

Funders	Funder number
Israeli Atomic Energy Committee
Council for Higher Education
Planning and Budgeting Committee of the Council for Higher Education of Israel

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.",

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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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AU - Yardeni, Guy

AU - Meyerstein, Dan

AU - Mikhailovich-Jivin, Elena

AU - Kats, Lioubov

AU - Cohen, Haim

AU - Zilbermann, Israel

AU - Maimon, Eric

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

Abstract

Bibliographical note

Funding

Keywords

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