Photogeneration of Reactive . Its Reversible Coordination of CO2 and Activation of Aromatic C-H Bonds

Article abstract of DOI:10.1021/ja00392a023

Irradiation of (diphos = Ph2PCH2CH2PPh2) with UV light leads to elimination of H2 with a 366-nm quantum yield of 0.07 +/- 0.02.The initial photoproduct is or a solvated derivative, but this species is highly reactive and rapidly adds N2, CO, and C2H4 to give the known , , and derivatives.Photolysis in the presence of C2H2 gives a new species tentatively formulated as .Irradiation in the presence of CO2 yields the new formate complex, , which derives by reversible insertion of CO2 into the Re-H bond of .NMR evidence indicates that undergoes rapid but reversible ortho metalation and insertion into the C-H bonds of benzene. can also be generated via photoinduced loss of N2 from .