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]­[(RF)2M­(μ-PPh2)2M′(κ2,N,C-C13H8N)] (RF = C6F5; M = M′ = Pt, 1; M = Pt, M′ = Pd, 2; M = Pd, M′ = Pt, 3; M = M′ = Pd, 4), is described. Addition of I2 to 1–4 gives complexes [(RF)2MII(μ-PPh2)­(μ-I)­PdII{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/C∧N reductive coupling on the mixed valence M­(II)–M′(IV) [NBu4]­[(RF)2MII(μ-PPh2)2M′IV(κ2,N,C- C13H8N)­I2] complexes, which were identified for MII = Pd, M′IV = Pt (9), and isolated for MII = 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.