Issue 7, 2001

A study of the molecular and electronic structure of iron(ii) and ruthenium(ii) 1,3-di- and 1,2,4-tri-phospholyl sandwich compounds by photoelectron spectroscopy and density functional theory

Abstract

The synthesis and variable temperature 1H NMR spectrum of the new tetraphosphaferrocene [Fe(η5-P2C3Bu3t)2] are presented and the photoelectron spectra are reported for [Fe(η5-P3C2Bu2t)2] 1a, [Fe(η5-P2C3Bu3t)2] 2a, [Fe(η5-P2C3Bu3t)(η5-P3C2Bu2t)] 3a and [Ru(η5-P3C2Bu3t)2] 4a. Density functional calculations were used to optimise the geometry and calculate the ionization energies of the parent analogues. Good agreement was obtained with the experimental results, giving support to the theoretical modelling of these sandwich compounds. Analysis of their electronic structure showed that replacement of RC fragments by P atoms in the η5-ligated cyclopentadienyl rings increases their acceptor properties. Extensive σπ mixing makes the description of the orbitals complex. Some higher lying Pσ levels are found to have similar ionization energies to the d electrons.

Graphical abstract: A study of the molecular and electronic structure of iron(ii) and ruthenium(ii) 1,3-di- and 1,2,4-tri-phospholyl sandwich compounds by photoelectron spectroscopy and density functional theory

Article information

Article type
Paper
Submitted
27 Nov 2000
Accepted
24 Jan 2001
First published
09 Mar 2001

J. Chem. Soc., Dalton Trans., 2001, 1013-1022

A study of the molecular and electronic structure of iron(II) and ruthenium(II) 1,3-di- and 1,2,4-tri-phospholyl sandwich compounds by photoelectron spectroscopy and density functional theory

R. Bartsch, F. G. N. Cloke, J. C. Green, R. M. Matos, J. F. Nixon, R. J. Suffolk, J. L. Suter and D. J. Wilson, J. Chem. Soc., Dalton Trans., 2001, 1013 DOI: 10.1039/B009481L

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