Issue 4, 1986

He I and He II photoelectron spectra of some trifluorophosphine, carbonyl, and hydrido transition metal complexes

Abstract

The He I and He II gas-phase ultraviolet photoelectron (p.e.) spectra of [M(PF3)5](M = Fe or Ru), [ReH(PF3)5], and [RuH2(PF3)4], together with the He I spectrum of [OsH2(CO)4], have been recorded and assigned empirically. The highest energy bands, corresponding to ionisation from the σ(M-L) and ligand localised orbitals, are separated from the predominantly metal-based bands by bands associated with the metal–hydrogen bonding orbitals (where present). For the [M (PF3)5] complexes, evidence is presented for significant phosphorus character in the e′(highest occupied molecular orbital) level, indicating a greater metal–phosphorus interaction than is found for the e″(second highest occupied molecular orbital) level. The p.e. bands due to ionisation from the M-H localised orbitals of [OsH2(CO)4] occur at 11.1 and 11.5 eV, values significantly lower than those found for the bridging hydrido moieties of [Os3(µ-H)2(CO)10] and [Os4(µ-H)4(CO)12](12.1–12.8 eV). A comparison of the p.e. data reported herein with literature data reveals two trends: a trend towards increasing ionisation energy of the metal d bands in [M (PF3)x] complexes with the atomic number of M, and a trend towards lower ionisation energy for the σ(M—H) bands of PF3 complexes on descending a Group. This latter trend contrasts with the approximately constant, or slightly increasing, ionisation energy associated with the analogous bands of the related hydrido carbonyl complexes.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1986, 765-770

He I and He II photoelectron spectra of some trifluorophosphine, carbonyl, and hydrido transition metal complexes

J. F. Nixon, E. A. Seddon, R. J. Suffolk, M. J. Taylor, J. C. Green and R. J. Clark, J. Chem. Soc., Dalton Trans., 1986, 765 DOI: 10.1039/DT9860000765

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