Activation of C-F and C-H bonds by platinum in trifluorinated [C,N,N'] ligands. Crystal structures of [PtFMe(2){Me(2)NCH(2)CH(2)NHCH(CH(2)COMe)(2,4-C6H2F2)}] and [PtMe{Me(2)NCH(2)CH(2)N=CH(2,3,4-C6HF3)}]

Trifluorinated ligands Me(2)NCH(2)CH(2)N=CHR (R=2,4,6-C6H2F3 (2a), 2,3,6-C6H2Fe (2b)) react with [Pt(2)Me(4)(mu-SMe(2))(2)] (1) to yield the [C,N,N'] saturated cyclometalated platinum(IV) compounds [PtFMe(2){Me(2)NCH(2)CH(2)NHCH(CH(2)COMe)(C6H2F2)}] (4) arising from C-F bond activation followed by acetone addition on the iminic bond of the coordinated ligand. The reactions of the platinum substrate with trifluorinated ligands Me(2)NCH(2)CH(2)N=CHR (R=2,3,4-C6H2F3 (2c), 2,4,5-C6H2F3 (2d), 3,4,5-C6H2F3 (2e)) containing only one or no fluorine atom in the ortho positions yield the [C,N,N'] cyclometalated platinum(II) compounds [PtMe(Me(2)NCH(2)CH(2)N=CHC6HF3)] (5) by ortho metalation with loss of methane. Compounds 5 react with methyl iodide to yield the [C,N,N'] unsaturated cyclometalated platinum(IV) compounds [PtIMe(2)(Me(2)NCH(2)CH(2)N=CHC6HF3)] (6) and with triphenylphosphine to produce the displacement of the NMe(2) moiety and the formation of [C,N] cyclometalated compounds [PtMe(PPh(3))(Me(2)NCH(2)CH(2)N=CHC6HF3)] (7c). When there is a fluorine atom adjacent to platinum (F-5), the displacement of both nitrogen donor atoms takes place upon reaction with PPh(3) to yield the compounds [PtMe(PPh(3))(2)(Me(2)NCH(2)CH(2)N=CHC6HF3)] (7d,e). All compounds were characterized by elemental analyses and NMR spectroscopy, and [PtFMe(2){Me(2)NCH(2)CH(2)NHCH(CH(2)COMe)(2,4-C6H3F2)}] (4a) and [PtMe{Me(2)NCH(2)CH(2)N=CH(2,3,4-C6HF3)}] (5c) were characterized crystallographically.