Mechanism of reaction of alkyl radicals with copper(II)(glycylglycylglycine) in aqueous solutions

Corin Mansano-Weiss; Daniel M. Epstein; Haim Cohen; Alexandra Masarwa; Dan Meyerstein

doi:10.1016/s0020-1693(02)00950-7

Mechanism of reaction of alkyl radicals with copper(II)(glycylglycylglycine) in aqueous solutions

Corin Mansano-Weiss, Daniel M. Epstein, Haim Cohen, Alexandra Masarwa, Dan Meyerstein

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

13 Scopus citations

Abstract

The reactions of ·CH₃ and ·CH₂C(CH₃)₂OH with Cu(II)(GGG), GGG=glycylglycylglycine, in aqueous solutions were studied and compared with the analogous process for Cu(II)(glycine)₂. The mechanism involves the following steps:Cu(II)L+·R→LCu(III)R·R+LCu(II)-R→Cu(II)L+R ₂LCu(III)-R→(LCu(III)-R′)The heterolysis of the Cu(III)-CH₃ bond for (Gly)₂Cu(III)-CH₃ yields methane and Cu(III)(Gly)₂⁺ whereas that for (GGG)Cu(III)-CH₃ yields Cu(I)(GGG) and methanol. The LCu(III)-CH₂C(CH₃)₂OH complexes decompose viaLCu(III)-CH₂C(CH₃)₂OH→Cu(I)L+HOCH ₂C(CH₃)₂OHfollowed byCu(I)L+LCu(III)-CH₂C(CH₃)₂OH→Cu(II) L+LCu(II)-CH₂C(CH₃)₂OHLCu(II)-CH ₂C(CH₃)₂OH→Cu(II)L+CH₂=C (CH₃)₂+OH^-.The complex (GGG)Cu(III)-CH₃ decomposes slowly, k=0.0035 s^-1. Thus if analogous complexes are formed in biological systems they might react with other substrates present in the system yielding products which are deleterious to living species.

Original language	English
Pages (from-to)	283-291
Number of pages	9
Journal	Inorganica Chimica Acta
Volume	339
DOIs	https://doi.org/10.1016/s0020-1693(02)00950-7
State	Published - 15 Nov 2002
Externally published	Yes

Bibliographical note

Funding Information:
This study was supported in part by a grant from the Budgeting and Planning Committee of The Council of Higher Education and the Israel Atomic Energy Commission. D.M. wishes to thank the Alexander von Humboldt Foundation for support and Mrs. Irene Evens for her ongoing interest and support.

Funding

This study was supported in part by a grant from the Budgeting and Planning Committee of The Council of Higher Education and the Israel Atomic Energy Commission. D.M. wishes to thank the Alexander von Humboldt Foundation for support and Mrs. Irene Evens for her ongoing interest and support.

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

Keywords

Alkyl radicals
Biological ligands complexes
Copper complexes

Access to Document

10.1016/s0020-1693(02)00950-7

Cite this

@article{f60c820f8c8646a2ac7bb5eab497fec0,

title = "Mechanism of reaction of alkyl radicals with copper(II)(glycylglycylglycine) in aqueous solutions",

abstract = "The reactions of ·CH3 and ·CH2C(CH3)2OH with Cu(II)(GGG), GGG=glycylglycylglycine, in aqueous solutions were studied and compared with the analogous process for Cu(II)(glycine)2. The mechanism involves the following steps:Cu(II)L+·R→LCu(III)R·R+LCu(II)-R→Cu(II)L+R 2LCu(III)-R→(LCu(III)-R′)The heterolysis of the Cu(III)-CH3 bond for (Gly)2Cu(III)-CH3 yields methane and Cu(III)(Gly)2+ whereas that for (GGG)Cu(III)-CH3 yields Cu(I)(GGG) and methanol. The LCu(III)-CH2C(CH3)2OH complexes decompose viaLCu(III)-CH2C(CH3)2OH→Cu(I)L+HOCH 2C(CH3)2OHfollowed byCu(I)L+LCu(III)-CH2C(CH3)2OH→Cu(II) L+LCu(II)-CH2C(CH3)2OHLCu(II)-CH 2C(CH3)2OH→Cu(II)L+CH2=C (CH3)2+OH-.The complex (GGG)Cu(III)-CH3 decomposes slowly, k=0.0035 s-1. Thus if analogous complexes are formed in biological systems they might react with other substrates present in the system yielding products which are deleterious to living species.",

keywords = "Alkyl radicals, Biological ligands complexes, Copper complexes",

author = "Corin Mansano-Weiss and Epstein, {Daniel M.} and Haim Cohen and Alexandra Masarwa and Dan Meyerstein",

note = "Funding Information: This study was supported in part by a grant from the Budgeting and Planning Committee of The Council of Higher Education and the Israel Atomic Energy Commission. D.M. wishes to thank the Alexander von Humboldt Foundation for support and Mrs. Irene Evens for her ongoing interest and support. ",

year = "2002",

month = nov,

day = "15",

doi = "10.1016/s0020-1693(02)00950-7",

language = "אנגלית",

volume = "339",

pages = "283--291",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - Mechanism of reaction of alkyl radicals with copper(II)(glycylglycylglycine) in aqueous solutions

AU - Mansano-Weiss, Corin

AU - Epstein, Daniel M.

AU - Cohen, Haim

AU - Masarwa, Alexandra

AU - Meyerstein, Dan

N1 - Funding Information: This study was supported in part by a grant from the Budgeting and Planning Committee of The Council of Higher Education and the Israel Atomic Energy Commission. D.M. wishes to thank the Alexander von Humboldt Foundation for support and Mrs. Irene Evens for her ongoing interest and support.

PY - 2002/11/15

Y1 - 2002/11/15

N2 - The reactions of ·CH3 and ·CH2C(CH3)2OH with Cu(II)(GGG), GGG=glycylglycylglycine, in aqueous solutions were studied and compared with the analogous process for Cu(II)(glycine)2. The mechanism involves the following steps:Cu(II)L+·R→LCu(III)R·R+LCu(II)-R→Cu(II)L+R 2LCu(III)-R→(LCu(III)-R′)The heterolysis of the Cu(III)-CH3 bond for (Gly)2Cu(III)-CH3 yields methane and Cu(III)(Gly)2+ whereas that for (GGG)Cu(III)-CH3 yields Cu(I)(GGG) and methanol. The LCu(III)-CH2C(CH3)2OH complexes decompose viaLCu(III)-CH2C(CH3)2OH→Cu(I)L+HOCH 2C(CH3)2OHfollowed byCu(I)L+LCu(III)-CH2C(CH3)2OH→Cu(II) L+LCu(II)-CH2C(CH3)2OHLCu(II)-CH 2C(CH3)2OH→Cu(II)L+CH2=C (CH3)2+OH-.The complex (GGG)Cu(III)-CH3 decomposes slowly, k=0.0035 s-1. Thus if analogous complexes are formed in biological systems they might react with other substrates present in the system yielding products which are deleterious to living species.

AB - The reactions of ·CH3 and ·CH2C(CH3)2OH with Cu(II)(GGG), GGG=glycylglycylglycine, in aqueous solutions were studied and compared with the analogous process for Cu(II)(glycine)2. The mechanism involves the following steps:Cu(II)L+·R→LCu(III)R·R+LCu(II)-R→Cu(II)L+R 2LCu(III)-R→(LCu(III)-R′)The heterolysis of the Cu(III)-CH3 bond for (Gly)2Cu(III)-CH3 yields methane and Cu(III)(Gly)2+ whereas that for (GGG)Cu(III)-CH3 yields Cu(I)(GGG) and methanol. The LCu(III)-CH2C(CH3)2OH complexes decompose viaLCu(III)-CH2C(CH3)2OH→Cu(I)L+HOCH 2C(CH3)2OHfollowed byCu(I)L+LCu(III)-CH2C(CH3)2OH→Cu(II) L+LCu(II)-CH2C(CH3)2OHLCu(II)-CH 2C(CH3)2OH→Cu(II)L+CH2=C (CH3)2+OH-.The complex (GGG)Cu(III)-CH3 decomposes slowly, k=0.0035 s-1. Thus if analogous complexes are formed in biological systems they might react with other substrates present in the system yielding products which are deleterious to living species.

KW - Alkyl radicals

KW - Biological ligands complexes

KW - Copper complexes

UR - http://www.scopus.com/inward/record.url?scp=0037111934&partnerID=8YFLogxK

U2 - 10.1016/s0020-1693(02)00950-7

DO - 10.1016/s0020-1693(02)00950-7

M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???

AN - SCOPUS:0037111934

SN - 0020-1693

VL - 339

SP - 283

EP - 291

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Mechanism of reaction of alkyl radicals with copper(II)(glycylglycylglycine) in aqueous solutions

Abstract

Bibliographical note

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this