Matrix isolation and computational study of the thermal and photochemical reactions of CrCl2O2 with GeH4, AsH3 and SeH2

Matrix isolation has been combined with infrared spectroscopy and theoretical calculations to study intermediates formed in the thermal and photochemical reactions of CrCl2O2 with GeH4, AsH3 and H2Se in argon matrices. Photochemical reactions occurred for all 3 systems with light of λ > 300 nm, leading to multiple products with GeH4 and AsH3. For GeH4, O atom insertion into a Ge-H bond to form H3GeOH complexed to CrCl2O was observed, along with a novel product arising from H2 elimination, H2ClGe-O-CrCl2O. With AsH3, insertion to form the H2AsOH-CrCl2O complex was observed, along with valence expansion and O atom addition to form the H3AsO-CrCl2O complex. Product identification came through comparison to theoretical calculations at the B3LYP/6-311++g(d,2p) level, and through isotopic labeling for the arsenic system. Band intensities and product yields were sufficiently low with H2Se that only HSeOH-CrCl2O could be tentatively identified. Trends for O atom insertion versus O atom addition via valence expansion were explored.