Reactions of laser-ablated osmium and ruthenium atoms with nitrogen. Matrix infrared spectra and density functional calculations of osmium and ruthenium nitrides and dinitrides

Laser-ablated osmium and ruthenium atoms were reacted with nitrogen molecules; the products were isolated in solid argon and nitrogen and identified by infrared spectroscopy. Both MN and NMN nitrides are observed, and estimates for the triatomic bond angles are made using nitrogen and ruthenium isotopic data. The growth of NOsN on annealing in solid argon suggests that osmium atoms insert into the dinitrogen triple bond at cryogenic temperatures, allowing a lower limit of similar to 473 kJ/mol to be estimated for the average Os-N bond energy in NOsN. The force constants for MN and NMN (M= Fe, Ru, Os) were calculated using all available isotopic data; force constants increase moving down the metal group, and diatomic MN force constants are larger than those for the corresponding NMN triatomic molecules. DFT calculations for the ruthenium and osmium nitrides give reasonable agreement with experiment. Bonding analyses for these molecules show that the M-N bonds are largely nonpolar with bond orders in the range 2.5-3.0. Several metal dinitrogen complexes are also observed and assignments are proposed.