Chemical Reactivities of Coordinatively Unsaturated Hydridotris(phosphonite)cobalt(I) Species Photogenerated towards Allylic and Related Compounds

Article abstract of DOI:10.1246/bcsj.59.3925

Pyrex-filtered photoirradiation with a high-pressure Hg lamp was performed for a thermally inert hydridocobalt(I) CoH4 in the presence of some allylic compounds.Allyl benzoate and allyl phenyl ether showed the cleavage of allylic-O bonds to give propene in a stoichiometric quantity to the complex charged.Photoassisted catalytic double-bond migration occured for N-allylacetamide, N,N-diethylallylamine, and allylbenzene to afford the respective (E)- and (Z)-1-propenyl derivatives with kinetically controlled, E, Z compositions, and the fractions of Z isomers at the initial stage of the reaction proceeding were near 79, 30, and 20percent, respectively.Laser flash photolysis study revealed that the double-bond migration was initiated by the coordination of the substrates through C=C double bond rather than nitrogen or oxygen donor-atom to the coordinatively unsaturated species "CoH3" photogenerated.