Activation of Group 14 El−H Bonds at Platinum(0)

Acyclic hydrogermanes [Ar2GeH2; Ar = Ph (1), Mes (8)] and a hydrostannane (Ph2SnH2, 5) were reacted with the Pt(0) precursor (Ph3P)2Pt(η2-C2H4) (2). The mononuclear complexes (Ph3P)2Pt(H)(GePh2H) (3), (Ph3P)2Pt(H)(SnPh2H) (6), and (Ph3P)2Pt(H)(GeMes2H) (9) and the dinuclear complexes [(Ph3P)Pt(μ-η-H-GePh2)]2 (4) and [(Ph3P)2(H)Pt(μ-SnPh2)(μ-η2-H-SnPh2)Pt(PPh3)] (7) were formed in these reactions. The cyclic precursor 9,9-dihydrogermafluorene (Ar2GeH2; Ar2 = C12H8, 10) was prepared and also reacted with (Ph3P)2Pt(η2-C2H4). Mono-, di-, and trinuclear platinum−germanium products, (Ph3P)2Pt(H)[Ge(C12H8)H] (11), (Ph3P)2Pt[Ge(C12H8)H]2 (14), [(Ph3P)2(H)Pt(C12H8GeGeC12H8)Pt(H)(PPh3)2] (12), [(Ph3P)2(H)Pt(μ-GeC20H24)(μ-η2-H-GeC20H24)Pt(PPh3)] (15), and [(Ph3P)Pt(μ-GeC12H8)]3 (13), were identified as products from the reaction. Complexes containing Si−Pt, Ge−Pt, and Sn−Pt bonds were also formed via an exchange reaction starting from the dinuclear complex [(Ph3P)2(H)Pt(μ-SiC20H24)(μ-η2-H−SiC20H24)Pt(PPh3)] (16) and H2ElPh2 (El = Si, Ge), where the pre-existing bridging silicon groups were replaced with bridging (μ-η2-H-ElPh2) groups.