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Geometries and Electronic Structures of Group 10 and 11 Metal Carbonyl Cations, [M(CO)_n]^x⁺ (M^x⁺ = Ni²⁺, Pd²⁺, Pt²⁺, Cu⁺, Ag⁺, Au⁺; n = 1−4)

Koichi Mogi,*^† Yoshiko Sakai,^† Takaaki Sonoda,^† Qiang Xu,^‡ and Yoshie Souma^‡

Department of Molecular and Material Science, Kyushu University, 6-1 Kasuga Park, Kasuga, Hukuoka, 816-8580, Japan, and National Institute of Advanced Industrial Science and Technology, AIST, 1-8-31 Midorigaoka, Ikeda, Osaka, 563-8577, Japan

J. Phys. Chem. A, 2003, 107 (19), pp 3812–3821

DOI: 10.1021/jp0220534

Publication Date (Web): April 19, 2003

To whom correspondence should be addressed. Fax: +81-92-583-7459. E-mail: mogi@mm.kyushu-u.ac.jp.

†

Kyushu University.

‡

National Institute of Advanced Industrial Science and Technology.

Abstract

The geometry and electronic structure of group 10 and 11 metal carbonyl cations, [M(CO)_n]^x⁺ (M^x⁺ = Ni²⁺, Pd²⁺, Pt²⁺, Cu⁺, Ag⁺, Au⁺; n = 1−4), were examined by the hybrid density functional method (B3LYP) and the coupled cluster method (CCSD(T)). For group 10 metals, monocarbonyl cations have C_∞_v structures, dicarbonyl cations have D_∞_h and C₂_v structures, and tri- and tetracarbonyl cations have C₂_v and D₄_h structures, respectively. Group 11 metal carbonyl cations have C_∞_v, D_∞_h, D₃_h, and T_d structures for mono-, di-, tri-, and tetracarbonyls, respectively. The (CO)_n_-₁M^x⁺−CO dissociation energies D₀ (CO) of group 10 metal carbonyl cations are significantly larger than those of group 11 metal carbonyl cations. Group 10 metal tetracarbonyl cations are still stable, while for group 11 metals, D₀ (CO) is significantly reduced in going from dicarbonyls to tri- and tetracarbonyls. The vibrational frequencies ν(CO) are higher by 110−165 cm^-1 for group 10 metal complexes and by 45−115 cm^-1 for group 11 metal complexes than that for free CO (2143 cm^-1).