Document Detail


Synthesis and Characterization of Terminal [Re(XCO)(CO)(2) (triphos)] (X=N, P): Isocyanate versus Phosphaethynolate Complexes.
MedLine Citation:
PMID:  23019045     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The terminal rhenium(I) phosphaethynolate complex [Re(PCO)(CO)(2) (triphos)] has been prepared in a salt metathesis reaction from Na(OCP) and [Re(OTf)(CO)(2) (triphos)]. The analogous isocyanato complex [Re(NCO)(CO)(2) (triphos)] has been likewise prepared for comparison. The structure of both complexes was elucidated by X-ray diffraction studies. While the isocyanato complex is linear, the phosphaethynolate complex is strongly bent around the pnictogen center. Computations including natural bond orbital (NBO) theory, natural resonance theory (NRT), and natural population analysis (NPA) indicate that the isocyanato complex can be viewed as a classic Werner-type complex, that is, with an electrostatic interaction between the Re(I) and the NCO group. The phosphaethynolate complex [Re(PCO)(CO)(2) (triphos)] is best described as a metallaphosphaketene with a Re(I) -phosphorus bond of highly covalent character.
Authors:
Simone Alidori; Dominikus Heift; Gustavo Santiso-Quinones; Zoltán Benkő; Hansjörg Grützmacher; Maria Caporali; Luca Gonsalvi; Andrea Rossin; Maurizio Peruzzini
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-9-28
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  -     ISSN:  1521-3765     ISO Abbreviation:  Chemistry     Publication Date:  2012 Sep 
Date Detail:
Created Date:  2012-9-28     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Copyright Information:
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Affiliation:
Department of Chemistry and Applied Biology, ETH Zürich, 8093 Zürich (Switzerland), Fax: (+41) 44-633-10-32.
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