Abstract
The cyclometalated cationic Pd(II) and Pt(II) complexes [M(diphos)(CH2C6H2Me2P(Mes)(H))][X] (5−8: M = Pd, Pt; diphos = dppe (Ph2PCH2CH2PPh2), dppen (cis-Ph2PCHCHPPh2); Mes = 2,4,6-Me3C6H2; X = OTf, BF4) were prepared by thermolysis of the cations [M(diphos)(Me)(PMes2H)][X]. Deprotonation of 5−8 gave the neutral phosphido complexes M(diphos)(CH2C6H2Me2P(Mes)) (9−12); the Pd(II) compounds 9 and 11 are the first examples of stable palladium terminal phosphido alkyl complexes, and their crystal structures were determined. Fluxional processes in complexes 9−12 were studied by variable-temperature NMR spectroscopy; the spectra are consistent with low barriers to phosphorus inversion.
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