Synthesis of Neutral and Anionic Tetranuclear Clusters [Pt4(μ2-PPh2)3{μ3-PPh(1,2-η2-Ph)-κ3P}(C6F5)4L] and [NBu4][Pt4(μ2-PPh2)3{μ3-PPh(1,2-η2-Ph)-κ3P}(C6F5)5] Containing Five Coordinate P Atoms and Two Pt−Pt Bonds

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The reaction of [NBu 4 ] 2 [(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 Pt(μ-PPh 2 ) 2 Pt(C 6 F 5 ) 2 ] with cis -[Pt(C 6 F 5 ) 2 (thf) 2 ] (molar ratio 1:2) in CH 2 Cl 2 gives [NBu 4 ] 2 [Pt 2 (μ-C 6 F 5 ) 2 (C 6 F 5 ) 4 ] and [NBu 4 ][Pt 4 (μ-PPh 2 ) 4 (C 6 F 5 ) 5 ] ( 4 ). Its molecular X-ray structure reveals that it is a tetranuclear complex with two Pt−Pt bonds and an unusual μ 3 -PPh 2 ligand, which has a η 2 -phenyl interaction with one of the platinum centers. Complex 4 reacts with HClO 4 to form [Pt 4 (μ-PPh 2 ) 4 (C 6 F 5 ) 4 ], 5, which contains three Pt−Pt bonds and a μ 3 -PPh 2 bridging ligand. 5 reacts with L (L = PPh 3, py) to yield the neutral [Pt 4 (μ-PPh 2 ) 4 (C 6 F 5 ) 4 L] ( 6 and 7 ), with structures similar to 4 .