Initial and secondary intermediates in the reactions of OVCl3 and CrCl2O2 with H2O have been characterized by matrix isolation infrared spectroscopy and density functional calculations. Twin jet co-deposition of these reagents led to a series of infrared absorptions that are assigned to the 1:1 molecular complexes between these two species. Irradiation of these matrices with light of λ > 300 nm led to complete destruction of the bands of complexes, and the growth of a number of new bands. These are assigned to the Cl2V(O)OH and ClCr(O)2OH species, as well as to HCl arising from destruction of the complex. Identification of these species was supported by isotopic labeling (18O and 2H), as well as by B3LYP/6-311G+(d,2p) and B3LYP/LANL2DZ density functional calculations. Good agreement was observed between the experimental and computed frequencies. The overall yield of product was low for these system, and was probably a consequence of the low basicity of H2O.

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The matrix isolation technique has been combined with theoretical calculations to identify and characterize the photoproducts in the reaction of PH 3 with OVCl 3 and CrCl 2 O 2 . In contrast to previous studies, HCl elimination from an initial complex is not observed. Instead, a number of product bands, some quite intense, were observed and have been assigned to phosphine oxide, H 3 PO, through the direct O atom transfer from the transition metal oxo compound. This identification was supported by extensive isotopic labeling, and by comparison to theoretical calculations. H 3 PO formed in this manner is cage-paired and interacts with the transition metal fragment (VCl 3 or Cl 2 CrO), leading to a 113 cm -1 red-shift of the PdO stretching mode relative to isolated monomeric H 3 PO.

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Initial and secondary intermediates in the reaction of VCl 4 with NH 3 have been characterized by matrix isolation infrared spectroscopy and density functional calculations. Twin jet codeposition of these two reagents led to a series of moderately intense infrared absorptions that have been assigned to the 1:1 molecular complex between these two species. Irradiation of these matrices with light of λ > 300 nm led to complete destruction of the complex, and the growth of a number of new bands. These have been assigned to the Cl 3 VNH 2 species, complexed with a single HCl arising from destruction of the complex. Identification of these species (1:1 complex and photoproduct) was supported by extensive isotopic labeling ( 15 N and 2 H), as well as by B3LYP/ 6-311++g(d, 2p) density functional calculations. Good agreement was observed between the experimental and computed frequencies. The binding energy of the 1:1 complex was calculated to be ∆E°2 98 ) -11.43 kcal/mol at this level of theory. Similar experiments with (CH 3 ) 3 N led to no detectable products.