Photoinduced reactions of organic compounds with transition metal complexes

Activation of C−H Bonds by Metal Complexes

“…Both these tetramethyltin reactions model the interaction of the Pt(IV) + Pt(II) system with saturated hydrocarbons to a certain extent. The cleavage of the Sn−CH 3 bond by the PtCl 6 2- complex is accelerated by irradiation 61g. The formation of a σ-C 2 H 5 −PtCl 5 2- complex has been observed by 1 H NMR in the photochemical (CH 3 ) 2 (CH 2 CH 3 ) 2 Sn reaction in CD 3 COOD.…”

“…Complexes of types 33 or 35 can be easily prepared by the method initially described in ref c. According to this method, the chloride complex Pt II Cl 4 2- is reacted with an alkyl iodide at room temperature in aqueous solution to produce a σ-alkylplatinum(IV) complex.…”

“…According to this method, the chloride complex Pt II Cl 4 2- is reacted with an alkyl iodide at room temperature in aqueous solution to produce a σ-alkylplatinum(IV) complex. Methyl,61c ethyl, 61d,e and acetonyl 61f complexes of Pt(IV) have been prepared by this method. An interesting feature of the reaction is that the sixth coordination site in the octahedral product is occupied by water, while the I - ion is bound to another platinum(II) complex (PtI 2 and analogous products are formed and precipitate): …”

“…The acetonyl complex turned out to be the most stable, which is apparently due to the absence of β-hydrogens in its alkyl chain. 61d,e Indeed, the σ-ethyl derivative readily decomposed to produce a π-ethylene complex of Pt(II) in addition to the usual alcohol and alkyl chloride products. The reaction between PtCl 4 2- and n -hexyl iodide also produced a (1-hexene)platinum(II) π-complex 61e. Another method for forming σ-alkyl complexes of platinum(IV) is the reaction of PtCl 6 2- with certain alkyl derivatives of non-transition metals.…”

Unexpected, photochemically induced activation of the tetrabutylammonium cation by hexachloroplatinate(iv)

“…[PtCl 6] 2 is evidently the active agent, but it is not known to react thermally unless in the presence of acid. 13 However, there are reports of photochemical C H bond activation mediated by [PtCl6] 2 , 14 and control experiments then showed that formation of 1 did not proceed in the dark, rather occurring smoothly under UV irradiation (medium-pressure Hg discharge lamp) at room temperature in both acetone and CH2Cl2. 15 Thus, the success of reactions so far studied had resulted from the mediation of ambient light.…”