Document Detail

Are formal oxidation states above one viable in cyclopentadienylcopper cyanides?
MedLine Citation:
PMID:  21989958     Owner:  NLM     Status:  MEDLINE    
Recent experiments have led to the discovery of the thermally unstable organocopper compounds (η(3)-C(3)H(5))CuMe(2), [(η(3)-C(3)H(5))CuMe(3)](-), and CuMe (4)(-) in which the copper atom is in the +3 formal oxidation state. In a quest for more stable organocopper compounds with copper in formal oxidation states above one, the binuclear cyclopentadienylcopper cyanides Cp(2)Cu(2)(CN)(n) (Cp = η(5)-C(5)H(5); n = 1, 2, 3) have been studied using density functional theory (DFT). The lowest energy structures are found to have terminal Cp rings and bridging cyanide ligands up to a maximum of two bridges. Higher-energy Cp(2)Cu(2)(CN)(n) (n = 1, 2, 3) structures are found with bridging Cp rings. The Cp(2)Cu(2)(CN)(3) derivatives, with the copper atoms in an average +2.5 oxidation state, are clearly thermodynamically disfavored with respect to cyanogen loss. However, Cp(2)Cu(2)(CN)(2) and Cp(2)Cu(2)(CN), with the copper atoms in the average oxidation states +1.5 and +2, respectively, are predicted to have marginal viability. The prospects for the copper(II) derivative Cp(2)Cu(2)(CN)(2) contrast with that of the "simple" Cu(CN)(2), which is shown both experimentally and theoretically to be unstable with respect to cyanogen loss to give CuCN.
Congzhi Wang; Xiuhui Zhang; Qian-shu Li; Yaoming Xie; R Bruce King; Henry F Schaefer
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, Non-P.H.S.     Date:  2011-10-12
Journal Detail:
Title:  Journal of molecular modeling     Volume:  18     ISSN:  0948-5023     ISO Abbreviation:  J Mol Model     Publication Date:  2012 Jun 
Date Detail:
Created Date:  2012-05-28     Completed Date:  2012-09-20     Revised Date:  2013-03-15    
Medline Journal Info:
Nlm Unique ID:  9806569     Medline TA:  J Mol Model     Country:  Germany    
Other Details:
Languages:  eng     Pagination:  2387-98     Citation Subset:  IM    
Key Laboratory of Cluster Science, Ministry of Education of China, Department of Chemistry, Beijing Institute of Technology, Beijing, Peoples Republic of China.
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MeSH Terms
Coordination Complexes / chemistry*
Copper / chemistry*
Cyanides / chemistry*
Cyclopentanes / chemistry*
Models, Molecular
Molecular Conformation
Quantum Theory
Reg. No./Substance:
0/Coordination Complexes; 0/Cyanides; 0/Cyclopentanes; 7440-50-8/Copper

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