Reactions of laser-ablated ruthenium atoms with CO and H2 mixtures:: Infrared spectra and density functional theory calculations of H2Ru(CO)x (x=2-4) and (H2)RuCO

Reactions of laser-ablated ruthenium atoms with carbon monoxide and hydrogen in solid argon produce the unsaturated ruthenium carbonyl dihydride H2Ru(CO)(2) and the hydrogen complexes (H-2)(lambda)RuCO (x = 1, 2). The observed absorption bands of the reaction products are identified by isotopic substitution and reproduced well by DFT calculations of vibrational fundamentals. The growth of bands due to H2Ru(CO)(2) and (H-2)-RuCO during annealing in solid argon indicates that ruthenium monocarbonyl is coordinated with HL to form the dihydrogen complex (H-2)RuCO, while H2Ru(CO)(2) is formed from the (II)RuCO complex inserting into (Hz) upon coordinating with another CO. Weak bands due to H2Ru(CO)(3) and H2Ru(CO)(4) are also observed.