Combined DV-Xa and gas-phase UV photoelectron spectroscopic investigation of the electronic structures of tetravalent titanium, zirconium, molybdenum, and thorium 1-sila-3-metallacyclobutane metallocene complexes

Enrico Ciliberto, Santo Di Bella, Antonino Gulino, Ignazio Fragalá, Jeffrey L. Petersen, Tobin J Marks

Research output: Contribution to journalArticle

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Abstract

The electronic structures of the 1-sila-3-metallacyclobutane complexes, Cp2M(CH2SiMe2CH2), where Cp = η5-C5H5 and M = Ti, Zr, Mo, Th, have been investigated by a combination of SCF Hartree-Fock-Slater discrete variational Xα calculations and He I, He II UV photoelectron spectroscopy. Photoelectron data are completely consistent with the energy sequences and valence orbital atomic compositions determined by the theoretical calculations. It is found that these "stabilized" metallacyclobutane complexes are best described electronically as heterodinuclear molecules containing bridging μ-CH2 groups rather than simple strained hydrocarbyl derivatives. The formation of the four-membered ring involves bonding interactions analogous to those found in cyclobutane. The metal-ligand bonding involves stabilizing interactions between higher-lying empty orbitale of the bridging μ-CH2 groups and appropriate metal orbitals of the metallocene fragment The resulting higher-lying molecular orbitale representing the μ-C bonds have energies modulated by the relative amount of metal participation. More internal metallacycle molecular orbitals also provide a bonding contribution, although to a smaller extent The population of these orbitals causes a redistribution of electron densities and, in spite of the high formal metal oxidation state (+4), partially restores the d2 metal configuration. The 2 + 2 reactivity modes in the related metallacyclobutanes can be accounted for by analyzing the evolution of correlated molecular orbitals of Cp2Ti(CH2SiMe2CH2), Cp2TiCH2CH2CH2, Cp2Ti=CH2(C2H4), and of noninteracting Cp2Ti=CH2 + C2H4 molecules. The titanacyclobutane complex, Cp2TiCH2CH2CH2, can be considered as a latent olefin complex even though the metallacyclic structure is thermodynamically favored. Variation in orbital character and decreasing metal-d or -f covalency (with Ti ≥ Zr ≫ Th) of the LUMO in the corresponding 1-sila-3-metallacyclobutanes is closely connected with differences in reactivity.

Original languageEnglish
Pages (from-to)1727-1737
Number of pages11
JournalOrganometallics
Volume11
Issue number4
Publication statusPublished - 1992

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Thorium
Molybdenum
thorium
Photoelectrons
Titanium
Electronic structure
molybdenum
photoelectrons
titanium
Gases
Metals
vapor phases
electronic structure
metals
orbitals
Molecular orbitals
molecular orbitals
reactivity
Cyclobutanes
cyclobutane

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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Combined DV-Xa and gas-phase UV photoelectron spectroscopic investigation of the electronic structures of tetravalent titanium, zirconium, molybdenum, and thorium 1-sila-3-metallacyclobutane metallocene complexes. / Ciliberto, Enrico; Di Bella, Santo; Gulino, Antonino; Fragalá, Ignazio; Petersen, Jeffrey L.; Marks, Tobin J.

In: Organometallics, Vol. 11, No. 4, 1992, p. 1727-1737.

Research output: Contribution to journalArticle

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abstract = "The electronic structures of the 1-sila-3-metallacyclobutane complexes, Cp2M(CH2SiMe2CH2), where Cp = η5-C5H5 and M = Ti, Zr, Mo, Th, have been investigated by a combination of SCF Hartree-Fock-Slater discrete variational Xα calculations and He I, He II UV photoelectron spectroscopy. Photoelectron data are completely consistent with the energy sequences and valence orbital atomic compositions determined by the theoretical calculations. It is found that these {"}stabilized{"} metallacyclobutane complexes are best described electronically as heterodinuclear molecules containing bridging μ-CH2 groups rather than simple strained hydrocarbyl derivatives. The formation of the four-membered ring involves bonding interactions analogous to those found in cyclobutane. The metal-ligand bonding involves stabilizing interactions between higher-lying empty orbitale of the bridging μ-CH2 groups and appropriate metal orbitals of the metallocene fragment The resulting higher-lying molecular orbitale representing the μ-C bonds have energies modulated by the relative amount of metal participation. More internal metallacycle molecular orbitals also provide a bonding contribution, although to a smaller extent The population of these orbitals causes a redistribution of electron densities and, in spite of the high formal metal oxidation state (+4), partially restores the d2 metal configuration. The 2 + 2 reactivity modes in the related metallacyclobutanes can be accounted for by analyzing the evolution of correlated molecular orbitals of Cp2Ti(CH2SiMe2CH2), Cp2TiCH2CH2CH2, Cp2Ti=CH2(C2H4), and of noninteracting Cp2Ti=CH2 + C2H4 molecules. The titanacyclobutane complex, Cp2TiCH2CH2CH2, can be considered as a latent olefin complex even though the metallacyclic structure is thermodynamically favored. Variation in orbital character and decreasing metal-d or -f covalency (with Ti ≥ Zr ≫ Th) of the LUMO in the corresponding 1-sila-3-metallacyclobutanes is closely connected with differences in reactivity.",
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T1 - Combined DV-Xa and gas-phase UV photoelectron spectroscopic investigation of the electronic structures of tetravalent titanium, zirconium, molybdenum, and thorium 1-sila-3-metallacyclobutane metallocene complexes

AU - Ciliberto, Enrico

AU - Di Bella, Santo

AU - Gulino, Antonino

AU - Fragalá, Ignazio

AU - Petersen, Jeffrey L.

AU - Marks, Tobin J

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N2 - The electronic structures of the 1-sila-3-metallacyclobutane complexes, Cp2M(CH2SiMe2CH2), where Cp = η5-C5H5 and M = Ti, Zr, Mo, Th, have been investigated by a combination of SCF Hartree-Fock-Slater discrete variational Xα calculations and He I, He II UV photoelectron spectroscopy. Photoelectron data are completely consistent with the energy sequences and valence orbital atomic compositions determined by the theoretical calculations. It is found that these "stabilized" metallacyclobutane complexes are best described electronically as heterodinuclear molecules containing bridging μ-CH2 groups rather than simple strained hydrocarbyl derivatives. The formation of the four-membered ring involves bonding interactions analogous to those found in cyclobutane. The metal-ligand bonding involves stabilizing interactions between higher-lying empty orbitale of the bridging μ-CH2 groups and appropriate metal orbitals of the metallocene fragment The resulting higher-lying molecular orbitale representing the μ-C bonds have energies modulated by the relative amount of metal participation. More internal metallacycle molecular orbitals also provide a bonding contribution, although to a smaller extent The population of these orbitals causes a redistribution of electron densities and, in spite of the high formal metal oxidation state (+4), partially restores the d2 metal configuration. The 2 + 2 reactivity modes in the related metallacyclobutanes can be accounted for by analyzing the evolution of correlated molecular orbitals of Cp2Ti(CH2SiMe2CH2), Cp2TiCH2CH2CH2, Cp2Ti=CH2(C2H4), and of noninteracting Cp2Ti=CH2 + C2H4 molecules. The titanacyclobutane complex, Cp2TiCH2CH2CH2, can be considered as a latent olefin complex even though the metallacyclic structure is thermodynamically favored. Variation in orbital character and decreasing metal-d or -f covalency (with Ti ≥ Zr ≫ Th) of the LUMO in the corresponding 1-sila-3-metallacyclobutanes is closely connected with differences in reactivity.

AB - The electronic structures of the 1-sila-3-metallacyclobutane complexes, Cp2M(CH2SiMe2CH2), where Cp = η5-C5H5 and M = Ti, Zr, Mo, Th, have been investigated by a combination of SCF Hartree-Fock-Slater discrete variational Xα calculations and He I, He II UV photoelectron spectroscopy. Photoelectron data are completely consistent with the energy sequences and valence orbital atomic compositions determined by the theoretical calculations. It is found that these "stabilized" metallacyclobutane complexes are best described electronically as heterodinuclear molecules containing bridging μ-CH2 groups rather than simple strained hydrocarbyl derivatives. The formation of the four-membered ring involves bonding interactions analogous to those found in cyclobutane. The metal-ligand bonding involves stabilizing interactions between higher-lying empty orbitale of the bridging μ-CH2 groups and appropriate metal orbitals of the metallocene fragment The resulting higher-lying molecular orbitale representing the μ-C bonds have energies modulated by the relative amount of metal participation. More internal metallacycle molecular orbitals also provide a bonding contribution, although to a smaller extent The population of these orbitals causes a redistribution of electron densities and, in spite of the high formal metal oxidation state (+4), partially restores the d2 metal configuration. The 2 + 2 reactivity modes in the related metallacyclobutanes can be accounted for by analyzing the evolution of correlated molecular orbitals of Cp2Ti(CH2SiMe2CH2), Cp2TiCH2CH2CH2, Cp2Ti=CH2(C2H4), and of noninteracting Cp2Ti=CH2 + C2H4 molecules. The titanacyclobutane complex, Cp2TiCH2CH2CH2, can be considered as a latent olefin complex even though the metallacyclic structure is thermodynamically favored. Variation in orbital character and decreasing metal-d or -f covalency (with Ti ≥ Zr ≫ Th) of the LUMO in the corresponding 1-sila-3-metallacyclobutanes is closely connected with differences in reactivity.

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