Synthesis of a Square-Planar Rhodium Alkylidene N-Heterocyclic Carbene Complex and Its Reactivity Toward Alkenes

The first rhodium alkylidene square-planar complex stabilized by an N-heterocyclic carbene ligand, RhCl(CHPh)(IPr)PPh3 (2; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-carbene), has been prepared by reaction of RhCl(IPr)(PPh3)2 (1) with phenyldiazomethane and its dynamic behavior in solution stud...

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Bibliographic Details
Published inOrganometallics Vol. 30; no. 19; pp. 5208 - 5213
Main Authors Palacios, Laura, Miao, Xiaowei, Di Giuseppe, Andrea, Pascal, Simon, Cunchillos, Carmen, Castarlenas, Ricardo, Pérez-Torrente, Jesús J, Lahoz, Fernando J, Dixneuf, Pierre H, Oro, Luis A
Format Journal Article
LanguageEnglish
Published American Chemical Society 10.10.2011
Subjects
Catalysis
Chemical Sciences
Coordination chemistry
Inorganic chemistry
Organic chemistry
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Summary:The first rhodium alkylidene square-planar complex stabilized by an N-heterocyclic carbene ligand, RhCl(CHPh)(IPr)PPh3 (2; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-carbene), has been prepared by reaction of RhCl(IPr)(PPh3)2 (1) with phenyldiazomethane and its dynamic behavior in solution studied. Treatment of 2 with alkenes results in the formation of the η2-olefin complexes RhCl(η2-CH2CHR)(IPr)PPh3 (3, R = H; 4, R = Ph; 5, R = OEt) and new olefins arising from the coupling of the alkylidene with the alkenes, likely via a metallacyclobutane intermediate.
ISSN:0276-7333
1520-6041
DOI:10.1021/om2005782