B. Jedlicka et al., SYNTHESIS AND MOLECULAR-STRUCTURES OF PALLADIUM AND PLATINUM COMPLEXES OF PTFA - MODELS OF GRIGNARD CROSS-COUPLING CATALYSTS, Journal of organometallic chemistry, 516(1-2), 1996, pp. 97-110
A number of palladium(0) and palladium(II) as well as platinum(0) and
platinum(II) complexes of (eta(5)-cyclopentadienyl)-(eta(5)-4-endo-N,
phenylphosphino-4,5,6,7-tetrahydro-1H-indenyl)iron (PTFA) of the type
(PTFA)M(0)(alkene) and (PTFA)M(II)(R)X, (M = Pd, Pt; alkene = dibenzyl
ideneacetone, maleic anhydride, fumaronitrile and tetracyanoethylene;
R = CH3, Ph and PhCH(2); X = Cl, Br and I) have been synthesized as mo
dels of Grignard cross-coupling catalysts. All complexes were prepared
either by proper ligand exchange or via oxidative addition reactions.
A comparison of the X-ray structures of five complexes ((PTFA)Pd(fuma
ronitrile), 4, (PTFA)PdCl2, 8, (PTFA)Pd(Ph)I, 10, (PTFA)Pt(tetracyanoe
thylene), 6, and (PTFA)Pt(CH3)Cl, 13) showed that, in contrast to comp
lexes of -dimethylaminoethyl)-1-diphenylphosphino-ferrocene (PPFA), th
e overall molecular structures of PTFA complexes are comparable; they
neither strongly depend on the oxidation state of the metal nor on the
type of additional ligands coordinated to the metal, Compound 4, C32H
32FeN3PPd . CH2Cl2, crystallizes in the monoclinic space group P2(1)/c
(no. 14), with a = 19.237(2), b = 9.0737(10), c = 17.917(3) Angstrom,
beta = 96.458(11)degrees, V = 3107.6(7) Angstrom(3), Z = 4. The struc
ture refinement converged to R1 = 0.0579 for 3832 F-0 > 4 sigma(F-0) a
nd wR2 = 0.1276 for all 6520 unique data, S = 0.94. Compound 6, C34H30
FeN5PPt . C4H10O, crystallizes in the triclinic space group P (1) over
bar (no, 2), with a = 11.845(3), b = 12.120(4), c = 12.979(3) Angstro
m, alpha = 81.68(2)degrees, beta = 82.06(2)degrees, gamma = 68.11(3)de
grees, V = 1703.6(8) Angstrom(3), Z = 2. The structure refinement conv
erged to R1 = 0.0402 for 6459 F-0 > 4 sigma(F-0) and wR2 = 0.1076 for
all 7235 unique data, S = 1.04. Compound 13, C29H33ClFeNPPt, crystalli
zes in the monoclinic space group P2(1)/c (no. 14), with a = 16.122(2)
, b = 10.1608(11), c = 21.716(3) Angstrom, beta = 132.202(11)degrees,
V = 2635.2(5) Angstrom(3), Z = 4. The structure refinement converged t
o R1 = 0.0322 for 3846 F-0 > 4 sigma(F-0) and wR2 = 0.0734 for all 461
2 unique data, S = 1.03.