Hydrogen-Bond Acceptance of Bifunctional Ligands in an Alkyne-Metal Complex

J. Am. Chem. Soc., 130 (1), 20 -21, 2008. 10.1021/ja0774616 S0002-7863(07)07461-6
Web Release Date: December 8, 2007

Hydrogen-Bond Acceptance of Bifunctional Ligands in an Alkyne-Metal Complex

Douglas B. Grotjahn,* Valentín Miranda-Soto, Elijah J. Kragulj, Daniel A. Lev, Gülin Erdogan, Xi Zeng, and Andrew L. Cooksy

Department of Chemistry and Biochemistry, 5500 Campanile Drive, San Diego State University, San Diego, California 92182-1030

grotjahn@chemistry.sdsu.edu

Received September 27, 2007

Abstract:

Experiment and theory have been used to study reactive alkyne complexes, intermediates in anti-Markovnikov alkyne hydration by CpRu bis(phosphine) catalysts with heterocyclic substituents. Each heterocycle accepts a hydrogen bond from an acetylene C-H, as revealed by NMR coupling constants between alkyne ¹³C and ¹H nuclei as well as between alkyne ¹³C and pyridine ¹⁵N (^2hJ_CN). Moreover, further alkyne transformations occur at temperatures from 50 to 90 C below what is needed to convert a control compound without the heterocycles.

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