1,1'-Bis(diphenylphosphino)ferrocene complexes of platinum(II) and platinum(I). Crystal and molecular structure of [(L-L)Pt(.mu.-H)(.mu.-CO)Pt(L-L)][BF4].0.5H2O, where L-L = Fe(.eta.5-C5H4PPh2)2

Abstract

A series of platinum(II) derivatives with 1,1'-bis(dipheny1phosphino)ferrocene (L-L) were synthesized and characterized in solution mainly by 1 H and 31 P( 1 {H} NMR spectroscopy. The series includes, besides the known Pt(L-L)CI 2 ( 1 ), the mononuclear species Pt(L-L)(pz) 2 ( 2 , pzH = pyrazole), Pt(L-L)(3,5-Me 2 pz) ( 3 , 3,5-Me 2 pzH = 3,5-dimethylpyrazole), [Pt(L-L)(3,5-Me 2 pzH) 2 [BF 4 ] 2 ( 4 ), and [Pt(L-L)(H 2 O) 2 ][BF 4 ] 2 •χH 2 O ( 5 ) as well as the dinuclear species [(L-L)Pt(µ-OH) 2 Pt(L-L)][BF 4 ] 2 ( 6 ) and [Pt 2 (L-L) 2 H 3 ][BF 4 ] ( 7 ). Reaction of the hydrido complex 7 with CO (room temperature, 1 atm) gave [(L-L)Pt(µ-H)(µ-CO)Pt(L-L)][BF 4 ] ( 8 ), formally a platinum(I) derivative. The molecular structure of [(L-L)Pt(µ-H)(µ-CO)Pt(L-L)] [BF 4 ]•0.5H 2 O ( 8a ) was determined by X-ray analysis: the complex crystallizes in the triclinic space group P Ī with a = 12.411 (4) A, b = 15.930 (5) A, c = 16.922 (7) A, α = 100.64 (3)°, β = 98.74 (3)°, γ = 104.34 (3)°, Z = 2, and V = 3166 (4) A 3 . The structure was refined to a conventional R factor of 0.025. In the dinuclear cation, the platinum atoms have cis-square-planar coordination, which shows a significant distortion toward tetrahedral geometry with P–Pt–P angles of 103.68 (6) and 103.64 (6)°. The Pt–Pt distance is 2.790 A.