scalar relativistic study of the structure of rhodium acetate标量相对论研究醋酸铑的结构.pdfVIP

Int. J. Mol. Sci. 2004, 5, 67-74 International Journal of Molecular Sciences ISSN 1422-0067 © 2004 by MDPI /ijms/ Scalar Relativistic Study of the Structure of Rhodium Acetate 1* 2 Stephen D. Williams and Emily E. Edwards 1 Department of Chemistry, Appalachian State University, Boone, NC 28608, USA 2 Chemical Physics Program, University of Maryland, College Park, MD 20742, USA Tel.: 828-262-2965, Fax: 828-262-6558, E-mail: willsd@ * Author to whom correspondence should be addressed. Received: 30 April 2003 / Accepted: 24 July 2003 / Published: 30 January 2004 Abstract: Rhodium acetate, related rhodium carboxylates, and rhodium amide complexes are powerful catalysts for carbene chemistry. They readily promote the decomposition of diazo compounds and transfer the resulting carbene to a variety of substrates. There have been several quantum chemistry studies of these compounds, particularly of the acetate. These have all used non-relativistic methods, and all have shown optimized Rh-Rh bond lengths significantly longer than the experimental value. In this study we have surveyed several scalar relativistic DFT methods using Gaussian, Slater, and numerical basis functions (in DGAUSS, ADF, and DMOL3). Several combinations of exchange-correlation