Carbon-halide oxidative addition and carbon-carbon reductive elimination at a (PNP)Rh center

Sylvain Gatard; Remle Celenligil-Cetin; Chengyun Guo; Bruce M Foxman; Oleg V Ozerov

doi:10.1021/ja057948j

Carbon-halide oxidative addition and carbon-carbon reductive elimination at a (PNP)Rh center

J Am Chem Soc. 2006 Mar 8;128(9):2808-9. doi: 10.1021/ja057948j.

Authors

Sylvain Gatard¹, Remle Celenligil-Cetin, Chengyun Guo, Bruce M Foxman, Oleg V Ozerov

Affiliation

¹ Department of Chemistry, Brandeis University, MS015, 415 South Street, Waltham, MA 02454, USA.

PMID: 16506753
DOI: 10.1021/ja057948j

Abstract

An unsaturated (PNP)Rh fragment can be generated by means of C-C reductive elimination from (PNP)Rh(Me)(Ar) or (PNP)Rh(Ar)(Ar). This fragment undergoes carbon-halogen oxidative addition with aryl chlorides, bromides, and iodides at room temperature. The C-H oxidative addition products in reactions with haloarenes are not observed, and evidence is presented that carbon-halogen oxidative addition is thermodynamically preferred. C-C reductive elimination from (PNP)Rh(Me)(Ar) and (PNP)Rh(Ar)(Ar) proceeds near quantitatively as a clean, first-order reaction.