Document Detail

CO assisted N(2) functionalization activated by a dinuclear hafnium complex: a DFT mechanistic exploration.
MedLine Citation:
PMID:  23202291     Owner:  NLM     Status:  Publisher    
In this paper, the reaction mechanisms of CO assisted N(2) cleavage and functionalization activated by a dinuclear hafnium complex are studied using a density function theory (DFT) method. Several key intermediates (, , and ) with axial/equatorial N[double bond, length as m-dash]C[double bond, length as m-dash]O coordination structures are found to be of importance along reaction pathways of CO assisted N(2) functionalization, which could provide a profound theoretical insight into the C-N bond formation and N-N bond cleavage. There are two different attack directions to insert the first CO molecule into the Hf-N bonds of the dinuclear hafnium complex, which lead to C-N bond formation. The calculated results imply that CO insertion into the Hf(1)-N(3) bond (Path A1) reacts more easily than that into the Hf(2)-N(3) bond (Path A3). But for the insertion of the second CO insertion to give , there are two possibilities (Path A1 and Path A2) according to this insertion being after/before N-N bond cleavage. Two pathways (Path A1 and Path A2) are proved to be possible to form final dinitrogen functionalized products (oxamidide , and ) in this study, which explain the formation of different oxamidide isomers in CO assisted N(2) functionalization activated by a dinuclear hafnium complex.
Xuelu Ma; Xin Zhang; Wenchao Zhang; Ming Lei
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-11-30
Journal Detail:
Title:  Physical chemistry chemical physics : PCCP     Volume:  -     ISSN:  1463-9084     ISO Abbreviation:  Phys Chem Chem Phys     Publication Date:  2012 Nov 
Date Detail:
Created Date:  2012-12-3     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  100888160     Medline TA:  Phys Chem Chem Phys     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
State Key Laboratory of Chemical Resource Engineering, Institute of Materia Medica, College of Science, Beijing University of Chemical Technology, Beijing, 100029, People's Republic of China.
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