Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes.

Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes. Research Abstract Details 

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Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes. Abstract Text:

Hong-Chang Liang,Christiana Xin Zhang,Mark J Henson,Roger D Sommer,Karen R Hatwell,Susan Kaderli,Andreas D ,Arnold L Rheingold,Edward I Solomon,Kenneth D Karlin,

Copper(I)-dioxygen interactions are of great interest due to their role in biological O2-processing as well as their importance in industrial oxidation processes. We describe here the study of systems which lead to new insights concerning the factors which govern Cu(II)-mu-eta2:eta2 (side-on) peroxo versus Cu(III)-bis-mu-oxo species formation. Drastic differences in O2-reactivity of Cu(I) complexes which differ only by a single -CH3 versus -H substituent on the central amine of the tridentate ligands employed are observed. [Cu(MeAN)]B(C6F5)4 (1) (MeAN = N,N,N',N',N'-pentamethyl-dipropylenetriamine) reacts with O2 at -80 degrees C to form almost exclusively the side-on peroxo complex [{CuII(MeAN)}2(O2)]2+ (3) in CH2Cl2, tetrahydrofuran, acetone, and diethyl ether solvents, as characterized by UV-vis and resonance Raman spectroscopies. In sharp contrast, [Cu(AN)]B(C6F5)4 (2) (AN = 3, 3'-iminobis(N,N-dimethyl-propylamine) can support either Cu2O2 structures in a strongly solvent-dependent manner. Extreme behavior is observed in CH2Cl2 solvent, where 1 reacts with O2 giving 3, while 2 forms exclusively the bis-mu-oxo species [{CuIII(AN)}2(O)2]2+ (4Oxo). Stopped-flow kinetics measurements also reveal significant variations in the oxygenation reactions of 1 versus 2, including the observations that 4Oxo forms much faster than does 3; the former decomposes quickly, while the latter is quite stable at 193 K. The solvent-dependence of the bis-mu-oxo versus side-on peroxo preference observed for 2 is opposite to that reported for other known copper(I) complexes; the factors which may be responsible for the unusual behavior of 1/O2 versus 2/O2 (possibly N-H hydrogen bonding in the AN chemistry) are suggested. The factors which affect bis-mu-oxo versus side-on peroxo formation continue to be of interest.

Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes. Publishing Authors By Initials

HC Liang,CX Zhang,MJ Henson,RD Sommer,KR Hatwell,S Kaderli,AD ,AL Rheingold,EI Solomon,KD Karlin,

For similar inorganic chemicals: elements: chalcogens: oxygen research abstracts see: inorganic chemicals: elements: chalcogens: oxygen research

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Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes. Journal Published:

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Journal of the American Chemical Society

VOLUME: 124

Page Numbers: 4170-1

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 24

MONTH: Apr

YEAR: 2002

Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes. Information

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LANGUAGE: eng

NlmUniqueID: 7503056

Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes. Keywords Mesh Terms:

KEYWORDS: Oxygen

MESH TERMS: chemistry

Chemical & Substance for Abstract: Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes. Information

Substance Name: Oxygen

Registry Number: 7782-44-7

Grant and Affiliation Information for Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes.

AFFILIATION: Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM28962

ACRONYM: GM

MEDLINETA: J Am Chem Soc

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