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.

无环氢锗烷(Acyclic hydrogermanes，通式为Ar₂GeH₂，其中Ar为苯基(Ph，化合物1)、均三甲苯基(Mes，化合物8))与氢锡烷(hydrostannane，Ph₂SnH₂，化合物5)，分别与零价铂前驱体(Pt(0) precursor)——三苯基膦(PPh3)合铂(η²-乙烯)[(Ph₃P)₂Pt(η²-C₂H₄)，化合物2]发生反应。反应生成单核配合物(Ph₃P)₂Pt(H)(GePh₂H)（化合物3）、(Ph₃P)₂Pt(H)(SnPh₂H)（化合物6）与(Ph₃P)₂Pt(H)(GeMes₂H)（化合物9），同时得到双核配合物[(Ph₃P)Pt(μ-η²-H-GePh₂)]₂（化合物4）及[(Ph₃P)₂(H)Pt(μ-SnPh₂)(μ-η²-H-SnPh₂)Pt(PPh3)]（化合物7）。我们合成了环状前驱体9,9-二氢锗芴(9,9-dihydrogermafluorene，通式为Ar₂GeH₂，其中Ar₂为C₁₂H₈，化合物10)，并将其与(Ph₃P)₂Pt(η²-C₂H₄)进行反应。该反应的产物经鉴定为单、双及三核铂-锗配合物，包括(Ph₃P)₂Pt(H)[Ge(C₁₂H₈)H]（化合物11）、(Ph₃P)₂Pt[Ge(C₁₂H₈)H]₂（化合物14）、[(Ph₃P)₂(H)Pt(C₁₂H₈GeGeC₁₂H₈)Pt(H)(PPh3)₂]（化合物12）、[(Ph₃P)₂(H)Pt(μ-GeC₂₀H₂₄)(μ-η²-H-GeC₂₀H₂₄)Pt(PPh3)]（化合物15）以及[(Ph₃P)Pt(μ-GeC₁₂H₈)]₃（化合物13）。通过双核配合物[(Ph₃P)₂(H)Pt(μ-SiC₂₀H₂₄)(μ-η²-H-SiC₂₀H₂₄)Pt(PPh3)]（化合物16）与H₂ElPh₂（El=Si、Ge）的取代反应，同样可得到含Si-Pt、Ge-Pt及Sn-Pt键的配合物；反应中原有的桥联硅基团被桥联(μ-η²-H-ElPh₂)基团取代。