SYNTHESIS AND REACTIONS OF CATIONIC PALLADIUM AND PLATINUM CYCLOPENTADIENYL COMPLEXES - MOLECULAR-STRUCTURE OF BIS-(DIPHENYLPHOSPHINO)ETHANE]PLATINUM(II)TRIFLATE
S. Fallis et al., SYNTHESIS AND REACTIONS OF CATIONIC PALLADIUM AND PLATINUM CYCLOPENTADIENYL COMPLEXES - MOLECULAR-STRUCTURE OF BIS-(DIPHENYLPHOSPHINO)ETHANE]PLATINUM(II)TRIFLATE, Organometallics, 12(10), 1993, pp. 3851-3855
The palladium and platinum triflate complexes [M(OTf)2(P-P)] (P-P = dp
pm, dppe, dppp) react with cyclopentadienylthallium to produce the ion
ic, eta5-cyclopentadienyl complexes [M(eta5-C5H5)(P-P)]OTf, which are
isolated as air-stable solids. They have been characterized by NMR spe
ctroscopy, elemental analysis, and, in the case of [Pt(eta5-C5H5)(dppe
)]OTf, X-ray crystallography. The compound crystallizes in the monocli
nic space group P2(1) with a = 9.822(3) angstrom, b = 12.072(4) angstr
om, c = 13.702(5) angstrom, beta = 110.56(2)degrees, V = 1521.2(9) ang
strom3, and Z = 2. Least-squares refinement converged at R = 0.0390 an
d R(w) = 0.0516 based on 3819 reflections with F > 4.0sigma(F). In CDC
l3 solution [Pd(eta5-C5H5)(dppe)]+ reacts with PEt3 to give [PdCl(PEt3
)(dppe)]+, but in d6-acetone displacement of dppe occurs to produce [P
d(eta5-C5H5)(PEt3)2]+. The reaction of the dppm compound with PEt3 giv
es many products, whereas the reaction of [Pd(eta5-C5H5)(dppp)]+ is ve
ry slow. The reactions of [Pt(eta5-C5H5)(P-P)]+ (P-P = dppm, dppp) wit
h PEt3 are also very slow, but with the dppe complex two isomeric prod
ucts are obtained. These are identified from their NMR spectra as the
two possible sp2-bonded, eta1-cyclopentadienyl complexes [Pt(C5H5)-(PE
t3)(dppe)]+.