Formation of P-C Bond through Reductive Coupling Between Bridging Phosphido and Benzoquinolinate Groups. Isolation of Complexes of the Pt(II)/Pt(IV)/Pt(II) Sequence

The rational synthesis of dinuclear asymmetric phosphanido derivatives of palladium and platinum(II), [NBu4][(R-F)(2)M(mu-PPh2)(2)M'(kappa(2),N,C-C13H8N)] (R-F = C6F5; M = M' = Pt, 1; M = Pt, M' = Pd, 2; M = Pd, M' = Pt, 3; M = M' = Pd, 4), is described. Addition of I-2 to 1-4 gives complexes [(R-F)(2)M-II(mu-PPh2)(mu-I)Pd-II{PPh2(C13H8N)}] (M = M' = Pt, 6; M = Pt, M' = Pd, 7; M = M' = Pd, 8; M = Pd, M' = Pt 10) which contain the aminophosphane PPh2(C13H8N) ligand formed through a Ph2P/(CN)-N-boolean AND reductive coupling on the mixed valence M(II)-M'(IV) [NBu4][(R-F)(2)M-II(mu-PPh2)(2)M'(IV)(kappa(2),N,C- C13H8N)I-2] complexes, which were identified for M-II = Pd, M'(IV) = Pt (9), and isolated for M-II = Pt, M'(IV) = Pt (5). Complex 5 showed an unusual dynamic behavior consisting in the exchange of two phenyl groups bonded to different P atoms, as well as a "through space" spin-spin coupling between ortho-F atoms of the pentafluorophenyl rings.