Low temperature matrix photochemistry of M2(CO)4(μ-S-t-Bu)2 and [M(CO)2Cl2]1− anions, where M=Rh and Ir
摘要:
Photolysis of M-2(CO)(4)(mu-S-t-Bu)(2), where M = Rh or Ir, in Nujol matrices at ca. 90 K results in simple CO loss to form a tricarbonyl intermediate analogous to that observed for Rh-2(CO)(4)(mu-Cl)(2). Photolysis of the anions, [M(CO)(2)Cl-2](1-), where M = Rh or Ir, in inert ionic matrices at ca. 90 K, results in CO-loss to form an intermediate analogous to that formed by Rh(CO)(2)(i-Pr2HN)Cl. Finally, photolysis of trans-Ir(CO)(PMe3)(2)Cl in a Nujol matrix at ca. 90 K gives rise to a new species whose carbonyl band is shifted slightly down in energy as has been observed for trans-Rh(CO)(PMe3)(2)Cl. In all cases the iridium compounds behave similarly to the rhodium species although the photon energy for iridium photochemistry is typically above that of the rhodium compounds. (C) 2004 Elsevier B.V. All rights reserved.
Low temperature matrix photochemistry of M2(CO)4(μ-S-t-Bu)2 and [M(CO)2Cl2]1− anions, where M=Rh and Ir
摘要:
Photolysis of M-2(CO)(4)(mu-S-t-Bu)(2), where M = Rh or Ir, in Nujol matrices at ca. 90 K results in simple CO loss to form a tricarbonyl intermediate analogous to that observed for Rh-2(CO)(4)(mu-Cl)(2). Photolysis of the anions, [M(CO)(2)Cl-2](1-), where M = Rh or Ir, in inert ionic matrices at ca. 90 K, results in CO-loss to form an intermediate analogous to that formed by Rh(CO)(2)(i-Pr2HN)Cl. Finally, photolysis of trans-Ir(CO)(PMe3)(2)Cl in a Nujol matrix at ca. 90 K gives rise to a new species whose carbonyl band is shifted slightly down in energy as has been observed for trans-Rh(CO)(PMe3)(2)Cl. In all cases the iridium compounds behave similarly to the rhodium species although the photon energy for iridium photochemistry is typically above that of the rhodium compounds. (C) 2004 Elsevier B.V. All rights reserved.