Nonparameterized molecular orbital calculations and photoelectron spectroscopy of open- and closed-shell M(IV) M(η5-C5H5)2L2 complexes

Jeffrey L. Petersen, Dennis L Lichtenberger, Richard F. Fenske, Lawrence F. Dahl

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Abstract

Nonparameterized (Fenske-Hall)-type molecular orbital calculations have been performed on several d0, d1, and d2 M(IV) M(η5-C5H5)2L2 molecules, and the results have been found to be completely compatible with the interpretations obtained from the electron paramagnetic resonance and photoelectron spectral measurements as well as from the crystallographically acquired bond-length and bond-angle data. The MO calculations reveal that the LUMO for the d0 Ti(IV) complexes and the HOMO for the d1 and nonhydridic d2 M(IV) complexes possess analogous orbital characters principally associated with the metal dz2 and dx2-y2 AO's with considerable contributions from the 3p AO's of the sulfur or chlorine L ligands. The relative metal orbital compositions of the HOMO's in the open-shell d1 V(IV) complexes are in remarkable agreement with those obtained from our previously reported dilute single-crystal EPR studies on V(η5-C5H5)2S5 and V(η5-C5H4CH3)2Cl 2. For V(η5-C5H5)2S5 the per cent character ratio of 3dz2/3dx2-y2 = 12.7/1 (EPR) vs. 7.7/1 (MO), while the corresponding ratio of 20.0/1 from the EPR data on V(η5-C5H4CH3)2Cl 2 compares with that of 20.5/1 from the MO computations. Additional information concerning the electronic structure of M(η5-C5H5)2L2 complexes has been obtained from photoelectron spectroscopy. The PE spectra of M(η5-C5H5)2Cl2 and M(η5-C5H4CH3)2Cl 2 (where M = Ti, V) are presented and interpreted with the aid of the approximate MO calculations.

Original languageEnglish (US)
Pages (from-to)6433-6441
Number of pages9
JournalJournal of the American Chemical Society
Volume97
Issue number22
StatePublished - 1975
Externally publishedYes

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Photoelectron Spectroscopy
Orbital calculations
Molecular orbitals
Photoelectron spectroscopy
Paramagnetic resonance
Metals
Chlorine
Electron Spin Resonance Spectroscopy
Sulfur
Ligands
Bond length
Photoelectrons
Electronic structure
Single crystals
Molecules
Chemical analysis
oligomycin sensitivity-conferring protein

ASJC Scopus subject areas

  • Chemistry(all)

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Nonparameterized molecular orbital calculations and photoelectron spectroscopy of open- and closed-shell M(IV) M(η5-C5H5)2L2 complexes. / Petersen, Jeffrey L.; Lichtenberger, Dennis L; Fenske, Richard F.; Dahl, Lawrence F.

In: Journal of the American Chemical Society, Vol. 97, No. 22, 1975, p. 6433-6441.

Research output: Contribution to journalArticle

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title = "Nonparameterized molecular orbital calculations and photoelectron spectroscopy of open- and closed-shell M(IV) M(η5-C5H5)2L2 complexes",
abstract = "Nonparameterized (Fenske-Hall)-type molecular orbital calculations have been performed on several d0, d1, and d2 M(IV) M(η5-C5H5)2L2 molecules, and the results have been found to be completely compatible with the interpretations obtained from the electron paramagnetic resonance and photoelectron spectral measurements as well as from the crystallographically acquired bond-length and bond-angle data. The MO calculations reveal that the LUMO for the d0 Ti(IV) complexes and the HOMO for the d1 and nonhydridic d2 M(IV) complexes possess analogous orbital characters principally associated with the metal dz2 and dx2-y2 AO's with considerable contributions from the 3p AO's of the sulfur or chlorine L ligands. The relative metal orbital compositions of the HOMO's in the open-shell d1 V(IV) complexes are in remarkable agreement with those obtained from our previously reported dilute single-crystal EPR studies on V(η5-C5H5)2S5 and V(η5-C5H4CH3)2Cl 2. For V(η5-C5H5)2S5 the per cent character ratio of 3dz2/3dx2-y2 = 12.7/1 (EPR) vs. 7.7/1 (MO), while the corresponding ratio of 20.0/1 from the EPR data on V(η5-C5H4CH3)2Cl 2 compares with that of 20.5/1 from the MO computations. Additional information concerning the electronic structure of M(η5-C5H5)2L2 complexes has been obtained from photoelectron spectroscopy. The PE spectra of M(η5-C5H5)2Cl2 and M(η5-C5H4CH3)2Cl 2 (where M = Ti, V) are presented and interpreted with the aid of the approximate MO calculations.",
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T1 - Nonparameterized molecular orbital calculations and photoelectron spectroscopy of open- and closed-shell M(IV) M(η5-C5H5)2L2 complexes

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N2 - Nonparameterized (Fenske-Hall)-type molecular orbital calculations have been performed on several d0, d1, and d2 M(IV) M(η5-C5H5)2L2 molecules, and the results have been found to be completely compatible with the interpretations obtained from the electron paramagnetic resonance and photoelectron spectral measurements as well as from the crystallographically acquired bond-length and bond-angle data. The MO calculations reveal that the LUMO for the d0 Ti(IV) complexes and the HOMO for the d1 and nonhydridic d2 M(IV) complexes possess analogous orbital characters principally associated with the metal dz2 and dx2-y2 AO's with considerable contributions from the 3p AO's of the sulfur or chlorine L ligands. The relative metal orbital compositions of the HOMO's in the open-shell d1 V(IV) complexes are in remarkable agreement with those obtained from our previously reported dilute single-crystal EPR studies on V(η5-C5H5)2S5 and V(η5-C5H4CH3)2Cl 2. For V(η5-C5H5)2S5 the per cent character ratio of 3dz2/3dx2-y2 = 12.7/1 (EPR) vs. 7.7/1 (MO), while the corresponding ratio of 20.0/1 from the EPR data on V(η5-C5H4CH3)2Cl 2 compares with that of 20.5/1 from the MO computations. Additional information concerning the electronic structure of M(η5-C5H5)2L2 complexes has been obtained from photoelectron spectroscopy. The PE spectra of M(η5-C5H5)2Cl2 and M(η5-C5H4CH3)2Cl 2 (where M = Ti, V) are presented and interpreted with the aid of the approximate MO calculations.

AB - Nonparameterized (Fenske-Hall)-type molecular orbital calculations have been performed on several d0, d1, and d2 M(IV) M(η5-C5H5)2L2 molecules, and the results have been found to be completely compatible with the interpretations obtained from the electron paramagnetic resonance and photoelectron spectral measurements as well as from the crystallographically acquired bond-length and bond-angle data. The MO calculations reveal that the LUMO for the d0 Ti(IV) complexes and the HOMO for the d1 and nonhydridic d2 M(IV) complexes possess analogous orbital characters principally associated with the metal dz2 and dx2-y2 AO's with considerable contributions from the 3p AO's of the sulfur or chlorine L ligands. The relative metal orbital compositions of the HOMO's in the open-shell d1 V(IV) complexes are in remarkable agreement with those obtained from our previously reported dilute single-crystal EPR studies on V(η5-C5H5)2S5 and V(η5-C5H4CH3)2Cl 2. For V(η5-C5H5)2S5 the per cent character ratio of 3dz2/3dx2-y2 = 12.7/1 (EPR) vs. 7.7/1 (MO), while the corresponding ratio of 20.0/1 from the EPR data on V(η5-C5H4CH3)2Cl 2 compares with that of 20.5/1 from the MO computations. Additional information concerning the electronic structure of M(η5-C5H5)2L2 complexes has been obtained from photoelectron spectroscopy. The PE spectra of M(η5-C5H5)2Cl2 and M(η5-C5H4CH3)2Cl 2 (where M = Ti, V) are presented and interpreted with the aid of the approximate MO calculations.

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