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• W1988474613 endingPage "4695" @default.
• W1988474613 startingPage "4688" @default.
• W1988474613 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)5PMe3, cis-W(CO)4(PMe3)2, trans-W(CO)4(PMe3)2, and fac-W(CO)3(PMe3)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 ≈ fac-W(CO)3(PMe3)3 < W(CO)5PMe3 ≤ cis-W(CO)4(PMe3)2 < trans-W(CO)4(PMe3)2. For the first time, the phosphorus 2p spin−orbit components of the phosphine complexes have been resolved. The binding energies (or ionization potentials) in the spectra of both W 5d valence level and W 4f core level regions are shifted almost linearly to lower energy with each successive step of ligand substitution. The shift per phosphine substitution is 0.66 ± 0.03 eV for the W 5d ionizations and 0.76 ± 0.03 eV for the W 4f ionizations (ΔEvalence/ΔEcore = 0.86 ± 0.03). Similar linear shift trends are also found in the phosphorus 2p core level and phosphorus valence “lone-pair” ionizations. These data confirm the ligand additivity model predictions for these complexes." @default.
• W1988474613 created "2016-06-24" @default.
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• W1988474613 date "1999-09-29" @default.
• W1988474613 modified "2023-10-16" @default.
• W1988474613 title "Photoelectron Spectra of Trimethylphosphine-Substituted Tungsten Carbonyls: Ligand Field Effects, Ligand Additivity Effects, and Core−Valence Ionization Correlations" @default.
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• W1988474613 doi "https://doi.org/10.1021/ic9904687" @default.
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• W1988474613 hasPublicationYear "1999" @default.
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