Photochemical intermediates of trans-Rh(CO)L2Cl where L=PMe3, PBu3, and i-Pr2HN and cis-Rh(CO)2(i-Pr2HN)Cl in frozen organic glasses

International audience; The Nujol glass matrix photolyses of Rh(CO)(PMe3)2Cl (1), Rh(CO)(PBu3)2Cl (2), Rh(CO)2(i-Pr2HN)Cl (3), and Rh(CO)(i-Pr2HN)2Cl (4), have been examined. Phototolysis of 1 (λirr>400 nm) and 2 (350<λirr<400 nm) give new species, A, with carbonyl stretching bands slightly below the parent bands. In the case of 1 this species appears to give rise to a second product, C, upon either extended photolysis or annealing. High-energy photolysis of 1, 2, and 4, result in loss of CO and formation of an IR silent species, RhL2Cl. In the case of 1 a new carbonyl species, B, is observed upon high-energy photolysis or annealing of a matrix containing CO and Rh(PMe3)2Cl. B may be conver…