Trifluorinated ligands
Me2NCH2CH2NCHR (R =
2,4,6-C6H2F3 (2a),
2,3,6-C6H2F3
(2b))
react with
[Pt2Me4(μ-SMe2)2]
(1) to yield the [C,N,N‘] saturated cyclometalated
platinum(IV)
compounds
[PtFMe2{Me2NCH2CH2NHCH(CH2COMe)(C6H2F2)}]
(4) arising from CF bond
activation followed by acetone addition on the iminic bond of the
coordinated ligand. The
reactions of the platinum substrate with trifluorinated ligands
Me2NCH2CH2NCHR (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(Me2NCH2CH2NCHC6HF3)]
(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
[PtIMe2(Me2NCH2CH2NCHC6HF3)]
(6) and with triphenylphosphine to produce
the displacement of the NMe2 moiety and the formation of
[C,N] cyclometalated compounds
[PtMe(PPh3)(Me2NCH2CH2NCHC6HF3)]
(7c). When there is a fluorine atom adjacent
to
platinum (F5), the displacement of both nitrogen donor
atoms takes place upon reaction
with PPh3 to yield the compounds
[PtMe(PPh3)2(Me2NCH2CH2NCHC6HF3)]
(7d,e). All
compounds were characterized by elemental analyses and NMR
spectroscopy, and
[PtFMe2{Me2NCH2CH2NHCH(CH2COMe)(2,4-C6H2F2)}]
(4a) and
[PtMe{Me2NCH2CH2NCH(2,3,4-C6HF3)}] (5c) were characterized
crystallographically.