Abstract
Over the past few years there has been much interest in the photochemistry of ({eta}{sup 5}-C{sub 5}R{sub 5})ML{sub 2} and ({eta}{sup 5}-C{sub 5}R{sub 5})ML(H){sub 2} (M = Rh, Ir; R = H, CH{sub 3}; L = CO, PR{sub 3} olefin) complexes leading to intermolecular activation of hydrocarbon C-H bonds. Recently, theoretical models of methane C-H bond activation have arisen based on this premise, i.e., that a coordinatively unsaturated 16-electron ({eta}{sup 5}-C{sub 5}R{sub 5})ML complex is the key reactive intermediate. The authors present here a study of the solution photochemistry of ({eta}{sup 5}-C{sub 5}H{sub 5})Rh(CO){sub 2} in the presence of excess scavenging PPh{sub 3} ligand; the results show unequivocally that this photoreaction proceeds via an associative mechanism.
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