Infrared Spectra and Density Functional Calculations of RuCO+, OsCO+, Ru(CO)x, Os(CO)x, Ru(CO)x- and Os(CO)x- (x = 1−4) in Solid Neon

Laser-ablated ruthenium and osmium atoms, cations and electrons have been reacted with CO molecules during condensation in excess neon. The Ru(CO) x and Os(CO) x ( x = 1−5) molecules are formed during sample deposition or on annealing. The Ru(CO) x - and Os(CO) x - ( x = 1−4) anions are formed by electron capture, and the RuCO + and OsCO + cations are produced by metal cation reactions and identified from 13 CO and C 18 O isotopic substitution, density functional calculations, and behavior on doping with CCl 4 to serve as an electron trap. Density functional calculations predict these frequencies within 1% and the isotopic shifts for different C−O stretching modes within averages of 1 to 2 cm -1 including vibrational modes for both C 3 v and D 2 d tetracarbonyl anion structures.