Low-temperature reactions of atomic cobalt with CH2N2, CH4, CH3D, CH2D2, CHD3, CD4, H2, D2, and HD

Article abstract of DOI:10.1021/ja00109a024

Cobalt atoms react spontaneously with diazomethane in solid argon at 12 K to yield CoCH₂, N₂CoCH₂, and at least two (N₂)_xCoCH₂ complexes. CH₃CoH is formed when dihydrogen is cocondensed as a ternary reagent. Photolysis of CH₃CoH (λ ≥ 400 nm) gives the σ-complex Co(CH₄) as a spectroscopically detectable species. Photolysis of this complex using an ultraviolet source regenerates CH₃CoH. The σ-complex has the triply degenerate ν4(f2) absorption of methane at 1305.3 cm^-1 split into two peaks, suggesting C_3ν symmetry. Studies using isotopically labeled methane show that these σ-complexes do not have rigid structures. UV photolysis of a Co/H₂/Ar matrix at 12-15 K gives CoH₂. Co(H₂) complexes could not be detected. Photolysis of Co/D₂/Ar and Co/DH/Ar matrices gave CoD₂ and CoHD, respectively.