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)(2)Pt(eta(2)-C2H4) (2). The mononuclear complexes (Ph3P)(2)Pt(H)(GePh2H) (3), (Ph3P)(2)Pt(H)(SnPh2H) (6), and (Ph3P)(2)Pt(H)(GeMes(2)H) (9) and the dinuclear complexes [(Ph3P)Pt(mu-eta-H-GePh2)](2) (4) and [(Ph3P)(2)(H)Pt(mu-SnPh2)(mu-eta(2)-H-SnPh2)Pt(PPh3)] (7) were formed in these reactions. The cyclic precursor 9,9-dihydrogermafluorene (Ar2GeH2; Ar-2 = C12H8, 10) was prepared and also reacted with (Ph3P)(2)Pt(eta(2)-C2H4). Mono-, di-, and trinuclear platinum-germanium products, (Ph3P)(2)Pt(H)[Ge(C12H8)H] (11), (Ph3P)(2)Pt[Ge(C12H8)H](2) (14), [(Ph3P)(2)(H)Pt(C12H8GeGeC12H8)Pt(H)(PPh3)(2)] (12), [(Ph3P)(2)(H)Pt(mu-GeC20H24)(mu-eta(2)-H-GeC20H24)Pt(PPh3)] (15), and [(Ph3P)Pt(mu-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(mu-SiC20H24)(mu-eta(2)-H-SiC20H24)Pt(PPh3)] (16) and H(2)ElPh(2) (El = Si, Ge), where the pre-existing bridging silicon groups were replaced with bridging (mu-eta(2)-H-ElPh(2)) groups.