COORDINATION CHEMISTRY OF 1,1'-BIS(2-PYRIDYL)FERROCENE IN PALLADIUM(II) AND PLATINUM(II) COMPLEXES AND REACTION OF (BPF)PD(ME)CL WITH CO - X-RAY STRUCTURE OF (1,1'-BIS(2-PYRIDYL)FERROCENE)PD(ME)CL AND (1,1'-BIS(2-PYRIDYL)FERROCENE)[PTCL2(CH2=CH2)](2)

The coordination chemistry of the ligand 1, 1'-bis(2-pyridyl)ferrocene (BPF) towards palladium and platinum has been studied. The very stabl e complexes (BPF)Pd(Me)Cl and BPF[PtCl2(CH2 = CH2)](2) have been synth esized from (COD)Pd(Me)Cl and Zeise's salt respectively and characteri zed by H-1-,C-13-NMR, elemental analysis and single crystal X-ray dete rmination. The crystals of(BPF)Pd(Me)Cl crystallize in the monoclinic space group C2/c (No. 15) with a = 17.4681(9), b = 9.1112(6), c = 27.5 98(2) Angstrom, beta = 96.926(5)degrees, V = 4360.3(5) Angstrom(3), Z = 8. The structure refinement converged to R(1) = 0.042 for 3541 F-0 > 4 sigma(F-0) and wR(2) = 0.084 for all 4982 unique reflections. The X -ray structure shows a square planar palladium complex with the ligand coordinated in a bidentate way with a relatively large bite angle of 84.48(13)degrees. The crystals of BPF[PtCl2(CH2 = CH2)](2) have the sp ace group P2(1)/n with a = 13.8584(9), b = 13.128(3), c = 14.807(1) An gstrom and beta = 90.13(1)degrees, V = 2693.9(7) Angstrom(3), Z = 4. T he structure refinement converged to R = 0.043 for 4310 observed refle ctions. This structure contains two PtCl2(CH2 = CH2) fragments bridged by one BPF ligand. A fast CO insertion occurs into the palladium-meth yl bond of the complex (BPF)Pd(Me)Cl. When the product of this reactio n, (BPF)Pd(C(O)Me)Cl, is kept under an 13 atmosphere of (CO)-C-13, low temperature NMR and IR measurements show the presence of four complex es, which an (BPF)Pd(C(O)Me)Cl and probably (BPF)Pd(C(O)Me)(CO)Cl, cis - and trans-Pd-2(CO)(2)(C(O)Me)(2)Cl-2. Both the complexes (BPF)Pd(Me) Cl and (BPF)Pd(C(O)Me)Cl show a fluxional behaviour of the coordinated BPF ligand in solution on the NMR time scale, which involves the inte rconversion of two enantiomers of the complexes and the exchange of th e two pyridyl groups of the ligand. BPF[PtCl2(CH2 = CH2)](2), in which the ethylene is tightly coordinated to the metal centre, reacts with an additional BPF ligand to give the four-coordinated complex (BPF)PtC l2(CH2 = CH2).