The Photolysis of Chlorocarbonylbis(triphenylphosphine)iridium(I) in Chloroform

Abstract

Under 254 or 313 nm irradiation in chloroform, [IrCl(CO)(PPh3)2] is converted cleanly to [IrCl2(CO)H(PPh3)2] through the addition of HCl, produced photochemically. Under 254 nm irradiation, some of the reaction of [IrCl(CO)(PPh3)2] occurs by direct photolysis of chloroform, though a greater contribution arises from a reaction initiated through absorption of light by the metal complex. Under 313 nm irradiation, essentially all of the reaction is metal-initiated. The linear dependence of the reaction rate on light intensity and on the fraction of light absorbed by the Ir(I) complex as well as the lack of a deuterium isotope effect rule out a radical process. Instead it is proposed that an association complex between excited state [IrCl(CO)(PPh3)2] and CHCl3 leads to dissociation of a chlorine atom from CHCl3, yielding HCl after abstraction of a hydrogen from another CHCl3. HCl then adds to a ground state [IrCl(CO)(PPh3)2] complex.

Near-UV photolysis of μ-dibromotetrabromo- dipalladate(II) in chloroform

“…Chlorine abstraction from chloroalkanes by metal complexes has been seen in other systems [49,50], but the feasibility of chlorine atom transfer in this case clearly depends on the relative bond strengths for homolytic cleavage of the Pd-Cl and C-Cl bonds. In chloroform, the latter is 339 kJ M À1 [51], while the Pd-Cl bond energy in PdCl 2À 4 has been estimated to lie between 339 and 351 kJ M À1 [52].…”