Mono(pentamethylcyclopentadienyl)uranium(III) complexes: Synthesis, properties, and X-ray structures of ({eta}-C{sub 5}Me{sub 5})UI{sub 2}(THF){sub 3}, ({eta}-C{sub 5}Me{sub 5})UI{sub 2}(py){sub 3}, and ({eta}-C{sub 5}Me{sub 5})U[N(SiMe{sub 3}){sub 2}]{sub 2}
The uranium(III) iodide complex UI{sub 3}(THF){sub 4} reacts cleanly at ambient temperature with 1 equiv of sodium and potassium pentamethylcyclopentadienide salts in tetrahydrofuran to form the mono-ring uranium(III) complex ({eta}-C{sub 5}Me{sub 5})UI{sub 2}(THF){sub 3}(1). Additionally, reaction of UI{sub 3}(THF){sub 4} with 2 equiv or more of K(C{sub 5}Me{sub 5}) in THF solution leads to the formation of the bis-ring adduct ({eta}-C{sub 5}Me{sub 5}){sub 2}UI(THF) (2) in high yield. In the solid state 1 exhibits a pseudo-octahedral mer,trans ligand geometry with the C{sub 5}Me{sub 5} ligand occupying one axial position. U-I bond lengths range from 3.161(1) to 3.179(1){angstrom}, while U-O distances to the THF ligands lie in the range 2.496(8)-2.594(10){angstrom}. 1 also provides a convenient entry into a variety of other mono-ring complexes of uranium(III). In the presence of excess pyridine, the coordinated THF ligands of 1 are readily displaced for form the tris(tyridine) adduct ({eta}-C{sub 5}Me{sub 5})UI{sub 2}(py){sub 3}(3), which exhibits a mer,trans ligand geometry in the solid state similar to that of 1. Methathesis of the iodide ligands in 1 with 2 equiv of KN(SiMe{sub 3}){sub 2} affords the bis(amido) complex ({eta}-C{sub 5}Me{sub 5})U[N(SiMe{sub 3}){sub 2}]{sub 2}(4). An X-ray diffraction study of this molecule reveals that methyl groups from both amido ligands are involved in agostic interactions with the uranium-(III) center.
- Research Organization:
- Los Alamos National Lab., NM (US)
- OSTI ID:
- 20017493
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 4 Vol. 19; ISSN 0276-7333; ISSN ORGND7
- Country of Publication:
- United States
- Language:
- English
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