Alkyne-to-vinylidene transformation on trans-(Cl)Rh(phosphine)2: acceleration by a heterocyclic ligand and absence of bimolecular mechanism

Douglas B Grotjahn; Xi Zeng; Andrew L Cooksy

doi:10.1021/ja058736p

Alkyne-to-vinylidene transformation on trans-(Cl)Rh(phosphine)2: acceleration by a heterocyclic ligand and absence of bimolecular mechanism

J Am Chem Soc. 2006 Mar 8;128(9):2798-9. doi: 10.1021/ja058736p.

Authors

Douglas B Grotjahn¹, Xi Zeng, Andrew L Cooksy

Affiliation

¹ Department of Chemistry and Biochemistry, 5500 Campanile Drive, San Diego State University, San Diego, CA 92182-1030, USA. [email protected]

PMID: 16506748
DOI: 10.1021/ja058736p

Abstract

Alkyne-to-vinylidene transformation on square-planar trans-(Cl)Rh(phosphine)2 has been proposed to proceed by a mechanism with a key step being bimolecular transfer of hydridic H to an alkynyl carbon. Labeling studies reported here are inconsistent with this pathway. In addition, an imidazolyl substituent accelerates the transformation.