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The reaction of ((eta)-Arene)Cr(CO)(,2)(CX) (X = S, Se) complexes with excess (RO)(,3)P (R = Me, Et, n-Bu, Ph) yields Cr(CO)(,2)(CX) (RO)(,3)P (,3), predominantly as the mer I isomer, in which a phosphite ligand is trans to CX. Arene displacement from ((eta)-C(,6)H(,6))Cr(CO)(,2)(CX) by tridentate phosphine ligands L-L-L L-L-L = (Me)C(CH(,2)P(Ph)(,2))(,3), (Ph(,2)PCH(,2)CH(,2))(,2)PhP gives fac-(L-L-L)Cr(CO)(,2)(CX) products. The molecular structures of Cr(CO)(,2)(CX) (MeO)(,3)P (,3) have been determined by single crystal X-ray diffraction. Intramolecular isomerization of these complexes as well as their tricarbonyl analogue has been demonstrated and activation parameters have been calculated for the rearrangement processes. Two-dimensional ('31)P NMR spectroscopy has provided evidence that isomerization occurs via trigonal prismatic intermediates. Kinetic investigations of the reaction of ((eta)-C(,6)H(,6))Cr(CO)(,2)(CX) with (MeO)(,3)P have established a first-order rate dependence on both the complex and the entering ligand. The faster reaction rate of the selenocarbonyl derivative relative to its thiocarbonyl analogue originates in a lower entropy of activation in the former case. The effect on the reaction rate of variation in the nature of the arene and of the entering ligand has been investigated. / An approach to hormonal receptor assay involving the detection by FT-IR spectroscopy of Cr(CO)(,3)-labelled modified estradiol bound to estrogen receptors in target tissue is reported. / The FT-IR spectra of FeTPP(CX) FeTPP = (5,10,15,20-tetraphenyl-porphinato)Fe(II); X = S, Se and FeTPP(CX)L (X = S, Se; L = pyridine, ethanol) have been obtained. Some changes in the porphyrin spectrum were observed with variation or removal of L, but not with variation of X.

Graduate

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Graduate / 0485