PtIPtI bond energy in dinuclear PtI complexes. A theoretical study》.pdf

15August 1997 CHEMICAL PHYSICS LETTERS ELSEVIER Chemical Physics Letters 274 (1997) 543-548 ptI-pt I bond energy in dinuclear Pt I complexes. A theoretical study Manabu Sugimoto, Fumiko Horiuchi, Shigeyoshi Sakaki Department of Applied Chemistry and Biochemistry Facul~ of Engineering, Kumamoto Universi~, Kurokami, Kumamoto 860, Japan Received 12 May 1997; in final form 4 June 1997 Abstract The metal-metal bond of [Pt2C12(CO)4] and [Pt2C14(CO)2]2- is investigated with the ab initio MO/MP2 method. The Pt~-Pt I bond energy (AE) is calculated to be 39-58 kcal/mol, being much larger than those for Pt°-Pt ° and ptII-pt H reported previously. In [Pt2C14(CO)2]2-, a negative A E is obtained without considering a countercation. The effect of the cation can be simulated by a positive point charge, and the point-charge dependence of AE can be derived by considering the electrostatic interactions by perturbation theory. Thus, it is concluded that an electrostatic potential due to countercations must be taken into account to estimate correctly the Pt-Pt bond energy. © 1997 Elsevier Science B.V. 1. Introduction able estimate of the d 9 metal-metal binding energy