Infrared Photodissociation Spectroscopy of Dinuclear Vanadium-Group Metal Carbonyl Complexes: Diatomic Synergistic Activation of Carbon Monoxide.

The geometric structure and bonding features of dinuclear vanadium-group transition metal carbonyl cation complexes in the form of VM(CO) n + ( n = 9-11, M = V, Nb, and Ta) are studied by infrared photodissociation spectroscopy in conjunction with density functional calculations. The homodinuclear V 2 (CO) 9 + is characterized as a quartet structure with C S symmetry, featuring two side-on bridging carbonyls and an end-on semi-bridging carbonyl. In contrast, for the heterodinuclear VNb(CO) 9 + and VTa(CO) 9 + , a C 2V sextet isomer with a linear bridging carbonyl is determined to coexist with the lower-lying C S structure analogous to V 2 (CO) 9 + . Bonding analyses manifest that the detected VM(CO) 9 + complexes featuring an (OC) 6 M-V(CO) 3 pattern can be regarded as the reaction products of two stable metal carbonyl fragments, and indicate the presence of the M-V d-d covalent interaction in the C S structure of VM(CO) 9 + . In addition, it is demonstrated that the significant activation of the bridging carbonyls in the VM(CO) 9 + complexes is due in large part to the diatomic cooperation of M-V, where the strong oxophilicity of vanadium is crucial to facilitate its binding to the oxygen end of the carbonyl groups. The results offer important insight into the structure and bonding of dinuclear vanadium-containing transition metal carbonyl cluster cations and provide inspiration for the design of active vanadium-based diatomic catalysts.