Theoretical Study for the Site Exchange Mechanism of Anionic 5-Coordinate Pt(II) Complexes with Halide, [PtX(hfac)2]- (X = Cl, Br, I, hfac = hexafluoroacetylacetonate)

Seichi OKEYAa*, Kan WAKAMATSUb, Takashi SHIBAHARAb, Hideo YAMAKADOa and Kichisuke NISHIMOTOb

aDepartment of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University
Sakaedani, Wakayama 640-8510, Japan
bDepartment of Chemistry, Faculty of Science, Okayama University of Science
Ridai-cho, Okayama 700-0005, Japan
*e-mail: okeya@sys.wakayama-u.ac.jp

(Received: May 24, 2002; Accepted for publication: August 5, 2002; Published on Web: September 11, 2002)

DFT calculations of the intra molecular site exchange process in square pyramidal five coordinate complexes, [PtX(hfac)2]- (hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, X = Cl, Br, I), were performed. The calculation reproduces well the X-ray molecular structures and the trigonal bipyramidal transition state energies of three possible paths, two of which actually seem to function, show that the order of the trans effect of halide ligands is Cl < Br < I, and that of the cis effect is Cl > Br > I, which is in accordance with the experimental results.

Keywords: DFT calculations, 5-Coordinate Pt(II) complex, Site exchange, trans effect, cis effect

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