Synthesis, single crystal X-ray structure determination and NMR studies of Cp2Fe(PPh2)2PtPh2 and Cp2Fe(PPh2)2PtI2

Diphenyl[1,1'-bis(diphenylphosphino)ferrocene]platinum(II) Cp2Fe(PPh2)(2)PtPh2 (I) and diiodo[1,1'-bis(diphenylphosphino)ferrocene]platinum(II) , Cp2Fe(PPh2)(2)PtI2 (2) were synthesized in nearly quantitative yield, with excellent purity by allowing Cp2Fe(PPh2)(2) to react with (COD)PtPh2 and (COD)PtI2 (COD = 1,5-cyclooctadiene), respectively. Compounds 1 and 2 have been well characterized by various analytical and spectroscopic techniques and also by single crystal X-ray diffraction. Platinum in both the complexes seemed to have a distorted square planar geometry. Interestingly, the respective bite angles (P-Pt-P bond angle) in 1 (101.2(1) Angstrom) and 2 (100.6(1)Angstrom) deviate from the ideal 90 degrees situation and are larger than in the reported structure, dppfPtCl(2) [dppf = 1,1'-bis(diphenylphosphino)ferrocene]. A detailed NMR study, including 2D and simulation experiments has been performed on these compounds for complete structural assignment. The compounds 1 and 2 crystallized in triclinic space groups P (1) over bar and P (1) over bar with a = 12.268(2) Angstrom, 10.089 (1); b = 13.043(2) Angstrom, 10.856 (1); c = 13.649(1), 17.787(1) Angstrom; alpha = 100.49(1), 86.75(1)degrees; beta = 93.12(1), 77.52(1)degrees; gamma = 103.44(1), 64.91(1)degrees; V= 2078.0(5), 1721.3(3) A(3) and Z= 2 and 2, respectively. The final refinements of 1 and 2 converged at R = 0.0388 and 0.0580, respectively. (C) 1998 Elsevier Science S.A. All rights reserved.