### Abstract

The electronic structure of the phosphathoracyclobutane Cp′_{2}Th(CH_{2}PMeCH_{2}) complex (Cp′ = η^{5}-Me_{5}C_{5}) has been investigated by a combination of ab initio relativistic effective core potential calculations for geometry optimization, DV-Xα calculations, and UV photoelectron spectroscopy. The formation of the four-membered ring involves bonding interactions analogous to those found in cyclobutane. Metal-ligand bonding involves both 5f and 6d metal atomic orbitals with a major role of the latter. The gas-phase UV photoelectron spectrum has been assigned using both comparative arguments and TSIE values obtained from DV-Xα calculations, as well as PE data on the closely related Cp′_{2}Th(CH_{2}SiMe_{2}CH_{2}) complex. The optimized structure is indicative of a slightly puckered four-membered metallacyclic ring having the P-CH_{3} vector in an endocyclic axial orientation. The structure shows close analogies with diffraction data for the related Cp′_{2}Th(CH_{2}SiMe_{2}CH_{2}) complex. According with NMR data, a single energy minimum has been found for the conformation with smaller intraligand repulsive interactions involving the P_{3p} lone pair.

Original language | English |
---|---|

Pages (from-to) | 3326-3332 |

Number of pages | 7 |

Journal | Organometallics |

Volume | 12 |

Issue number | 8 |

Publication status | Published - 1993 |

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### ASJC Scopus subject areas

- Inorganic Chemistry
- Organic Chemistry

### Cite this

^{5}-pentamethylcyclopentadienyl)phosphathoracyclobutane by relativistic ab initio, multipolar DV-Xa calculations and gas-phase UV photoelectron spectroscopy.

*Organometallics*,

*12*(8), 3326-3332.

**Photoelectron spectroscopy of f-element organometallic complexes. 10. Investigation of the electronic structure and geometry of bis(η ^{5}-pentamethylcyclopentadienyl)phosphathoracyclobutane by relativistic ab initio, multipolar DV-Xa calculations and gas-phase UV photoelectron spectroscopy.** / Di Bella, Santo; Gulino, Antonino; Lanza, Giuseppe; Fragalà, Ignazio L.; Marks, Tobin J.

Research output: Contribution to journal › Article

^{5}-pentamethylcyclopentadienyl)phosphathoracyclobutane by relativistic ab initio, multipolar DV-Xa calculations and gas-phase UV photoelectron spectroscopy',

*Organometallics*, vol. 12, no. 8, pp. 3326-3332.

^{5}-pentamethylcyclopentadienyl)phosphathoracyclobutane by relativistic ab initio, multipolar DV-Xa calculations and gas-phase UV photoelectron spectroscopy. Organometallics. 1993;12(8):3326-3332.

}

TY - JOUR

T1 - Photoelectron spectroscopy of f-element organometallic complexes. 10. Investigation of the electronic structure and geometry of bis(η5-pentamethylcyclopentadienyl)phosphathoracyclobutane by relativistic ab initio, multipolar DV-Xa calculations and gas-phase UV photoelectron spectroscopy

AU - Di Bella, Santo

AU - Gulino, Antonino

AU - Lanza, Giuseppe

AU - Fragalà, Ignazio L.

AU - Marks, Tobin J

PY - 1993

Y1 - 1993

N2 - The electronic structure of the phosphathoracyclobutane Cp′2Th(CH2PMeCH2) complex (Cp′ = η5-Me5C5) has been investigated by a combination of ab initio relativistic effective core potential calculations for geometry optimization, DV-Xα calculations, and UV photoelectron spectroscopy. The formation of the four-membered ring involves bonding interactions analogous to those found in cyclobutane. Metal-ligand bonding involves both 5f and 6d metal atomic orbitals with a major role of the latter. The gas-phase UV photoelectron spectrum has been assigned using both comparative arguments and TSIE values obtained from DV-Xα calculations, as well as PE data on the closely related Cp′2Th(CH2SiMe2CH2) complex. The optimized structure is indicative of a slightly puckered four-membered metallacyclic ring having the P-CH3 vector in an endocyclic axial orientation. The structure shows close analogies with diffraction data for the related Cp′2Th(CH2SiMe2CH2) complex. According with NMR data, a single energy minimum has been found for the conformation with smaller intraligand repulsive interactions involving the P3p lone pair.

AB - The electronic structure of the phosphathoracyclobutane Cp′2Th(CH2PMeCH2) complex (Cp′ = η5-Me5C5) has been investigated by a combination of ab initio relativistic effective core potential calculations for geometry optimization, DV-Xα calculations, and UV photoelectron spectroscopy. The formation of the four-membered ring involves bonding interactions analogous to those found in cyclobutane. Metal-ligand bonding involves both 5f and 6d metal atomic orbitals with a major role of the latter. The gas-phase UV photoelectron spectrum has been assigned using both comparative arguments and TSIE values obtained from DV-Xα calculations, as well as PE data on the closely related Cp′2Th(CH2SiMe2CH2) complex. The optimized structure is indicative of a slightly puckered four-membered metallacyclic ring having the P-CH3 vector in an endocyclic axial orientation. The structure shows close analogies with diffraction data for the related Cp′2Th(CH2SiMe2CH2) complex. According with NMR data, a single energy minimum has been found for the conformation with smaller intraligand repulsive interactions involving the P3p lone pair.

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M3 - Article

VL - 12

SP - 3326

EP - 3332

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 8

ER -