The geometries and electronic structures of group 10 metal binuclear carbonyl cations of [M2(CO)2]2+ and [M2(CO)6]2+ (M = Ni, Pd, and Pt) were studied using the B3YLP density functional theory. [M2(CO)2]2+ cations have two stable conformations; one is the CO-bridged structure in the D2h symmetry for M = Ni, and C2v symmetry for Pd and Pt, and the other is the linear structure in the Dooh symmetry. The former is more stable than the later for each of M = Ni, Pd, and Pt. The CO-bridged [M2(CO)2]2+ are characterized by σ-donation and π back-donation which lead to longer C-O bond lengths of (R(CO) = 1.130-1.137 Å) and lower CO vibrational frequencies of (v(CO)= 2055-2100cm-1) than those of free CO [R(CO)= 1.128 Å, v(CO)= 2143 cm-1], while the v(CO) is much higher than the values of the typical bridged metal carbonyls (1750-1850 cm-1). The linear [M2(CO)2]2+ have shorter R(CO)s (1.112-1.115 Å) and higher v(CO)s (2230-2260 cm-1) than those of free CO owing to the reduced w back-donation. [M2(CO)6]2+ cations have only one stable conformation (minimum) in the D2d symmetry, which contains two essentially planar tricarbonyl metal units that are linked via a metal-metal bond about which they are twisted by 90.0° with respect to each other. The R(CO)s (1.115-1.119 Å) are shorter and v(CO)s (21862240 cm-1) are higher than those of free CO. A transition state was found for [M2(CO) 6]2+ in which two carbonyls are symmetrically bridging onto two metals and the other four carbonyls are bound to each metal terminally with C2v symmetry. The R(CO)s for bridging CO are longer than those for terminal COs. The calculated v(CO)s for the CO-bridged [Pd2(CO)2]2+ and minimum [Pt2(CO)6] 2+ are in good agreement with available data given by IR and Raman spectroscopy for corresponding species. The bonding natures of M-C and C-O bonds are discussed in detail with reference to the molecular orbital energy diagrams, the results of population analysis, and the relativistic effects in metal atoms.
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