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Bond character between iron and phosphorus in Fe-P(E)YZ (E = O, S; Y, Z = alkoxy, amino, phenyl) as inferred from57Fe moessbauer measurements
A series of (eta5-C5R5)(CO)2Fe{P(E)YZ} complexes (R = H, Me; E = O, S; Y, Z = OMe, OEt, NEt2, MeNCH2CH2NMe, Ph), (eta5-C5R5)(CO)2FeX (X = Cl, Br, I), and (eta5-C5Me5)(CO)2FeCl were prepared, and the 57Fe Moessbauer spectra together with IR(nuCO) and 31P NMR spectra were measured. The Fe-P bond in (eta5-C5R5)(CO)2Fe{P(E)YZ} is found to be as covalent as the Fe-Me bond in (eta5-C5H5)Fe(CO)2Me. There are linear correlations between isomer shifts (IS) and quadrupole splittings (QS) in the 57Fe Moessbauer spectra, between IS and chemical shifts in the 31P NMR spectra (delta), between IS and the IR stretching frequencies in the CO region (nuCO)> and between delta and nuCO These correlations indicate that the electron-donating group on the phosphorus atom (Y, Z) increases the electron density on the phosphorus atom, increases pi-donation from P(E)YZ to the Fe, and concomitantly increases pi-back-donation from iron to the CO ligands. The systematic replacement of the carbonyl group by phosphine or phosphites shows the large shift in IS and QS, indicating a large change in the d-electron density of the iron atom. Especially for the complexes having no carbonyl ligand, the d-electron density is much accumulated on the iron atom.
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Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate