Syntheses of Dinuclear and Trinuclear Hydridoplatinum Complexes with Bridging Phosphido Ligands [Pt<sub>2</sub>H<sub>2</sub>(μ-PR<sub>2</sub>)<sub>2</sub>(PEt<sub>3</sub>)<sub>2</sub>] (R = <sup>t</sup>Bu, Ph) and [Pt<sub>3</sub>H<sub>2</sub>(μ-PPh<sub>2</sub>)<sub>4</sub>(PEt<sub>3</sub>)<sub>2</sub>]. Characterization of the Triangular Intermediate [Pt<sub>3</sub>H(μ-PPh<sub>2</sub>)<sub>3</sub>(PEt<sub>3</sub>)<sub>3</sub>] and Its Chemical Properties
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The reaction of Ph2PH with Pt(PEt3)3 in 2:1 molar ratio produces the linear triplatinum complex [Pt3H2(μ-PPh2)4(PEt3)2] (1). X-ray crystallography of 1 shows the structure of the complex with two PEt3 ligands at anti positions, while it exists as a mixture of the isomers with PEt3 at anti and syn positions. Pt(PEt3)3 reacts with equimolar Ph2PH to afford the dinuclear complex [Pt2H2(μ-PPh2)2(PEt3)2] (2) and the cyclic trinuclear complex [Pt3H(μ-PPh2)3(PEt3)3] (3) depending on the reaction conditions. A dinuclear platinum(II) complex with a structure similar to 2, [Pt2H2(μ-PtBu2)2(PEt3)2] (4), is obtained by the reaction of tBu2PH with Pt(PEt3)3. Isolated complexes 2 and 3 cleanly react with Ph2PH to form 1, indicating that the reaction of Ph2PH with Pt(PEt3)3, giving 1, involves these complexes as the intermediates. Complex 3 contains a triangular Pt3 core with Pt−Pt bonds in the range 2.9784(4)−2.9983(3) Å, as shown by X-ray crystallography. The 1H NMR spectrum of 3 exhibits the hydrido signal at δ −7.98 accompanied by splitting due to H−P and H−Pt coupling. Complex 3 reacts with Ph3SiH and Ph2SiH2 to give silylplatinum complexes [Pt3(SiHn+1Ph4-n)(μ-PPh2)3(PEt3)2] (5, n = 1; 6, n = 2). Cationic triangular complexes [Pt3(μ-PPh2)3(PEt3)3]+I- (7) and [Pt3(μ-PPh2)3(PEt3)3]+[B4O4Ar4(OH)]- (8, Ar = C6H4Me-4; 9, Ar = C6H4F-4; 10, Ar = C6H4CF3-4) are obtained from the reactions of complex 3 with MeI and with ArB(OH)2, respectively.
