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Photoelectron Spectra of Trimethylphosphine-Substituted Tungsten Carbonyls: Ligand Field Effects, Ligand Additivity
Jingcun Wu1, G. Michael Bancroft, Richard J. Puddephatt
1Department of Chemistry, University of Western Ontario, London, Ontario, Canada N6A 5B7, and Canadian Synchrotron Radiation Facility, University of Wisconsin-Madison, Stoughton, Wisconsin 53589.
Abstract:
High-resolution broad-scan gas-phase photoelectron spectra using synchrotron radiation (including valence, inner valence, and core levels) are reported for a series of trimethylphosphine-substituted tungsten carbonyls: W(CO)(6), W(CO)(5)PMe(3), cis-W(CO)(4)(PMe(3))(2), trans-W(CO)(4)(PMe(3))(2), and fac-W(CO)(3)(PMe(3))(3). The inner valence and core level spectra are interpreted by comparison with the published spectra of W(CO)(6) and other metal carbonyls. High-resolution valence level spectra of these complexes are also obtained by He I radiation. Fine structure, resulting from spin-orbit splitting, ligand field splittings, and vibrational coupling is resolved in the spectra of both W 5d and W 4f regions. Ligand field splittings on both the W 5d and W 4f levels increase in the order W(CO)(6) approximately fac-W(CO)(3)(PMe(3))(3) < W(CO)(5)PMe(3)