### 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 |
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Pages (from-to) | 3326-3332 |

Number of pages | 7 |

Journal | Organometallics |

Volume | 12 |

Issue number | 8 |

Publication status | Published - 1993 |

### ASJC Scopus subject areas

- Inorganic Chemistry
- Organic Chemistry

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## Cite this

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

*Organometallics*,

*12*(8), 3326-3332.