Bond character between iron and phosphorus in Fe-P(E)YZ (E = O, S; Y, Z = alkoxy, amino, phenyl) as inferred from57Fe mössbauer measurements

Hiroshi Nakazawa, Satoshi Ichimura, Yasushi Nishihara, Katsuhiko Miyoshi, Satoru Nakashima, Hiroshi Sakai

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Abstract

A series of (η5-C5R5)(CO)2Fe{P(E)YZ} complexes (R = H, Me; E = O, S; Y, Z = OMe, OEt, NEt2, MeNCH2CH2NMe, Ph), (η5-C5R5)(CO)2FeX (X = Cl, Br, I), and (η5-C5Me5)(CO)2FeCl were prepared, and the 57Fe Mössbauer spectra together with IR(νCO) and 31P NMR spectra were measured. The Fe-P bond in (η5-C5R5)(CO)2Fe{P(E)YZ} is found to be as covalent as the Fe-Me bond in (η5-C5H5)Fe(CO)2Me. There are linear correlations between isomer shifts (IS) and quadrupole splittings (QS) in the 57Fe Mössbauer spectra, between IS and chemical shifts in the 31P NMR spectra (δ), between IS and the IR stretching frequencies in the CO region (νCO)> and between δ and νCO These correlations indicate that the electron-donating group on the phosphorus atom (Y, Z) increases the electron density on the phosphorus atom, increases π-donation from P(E)YZ to the Fe, and concomitantly increases π-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.

Original languageEnglish
Pages (from-to)5061-5067
Number of pages7
JournalOrganometallics
Volume17
Issue number23
DOIs
Publication statusPublished - 1998
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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