skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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}

Abstract

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 frommore » both amido ligands are involved in agostic interactions with the uranium-(III) center.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Los Alamos National Lab., NM (US)
OSTI Identifier:
20017493
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 19; Journal Issue: 4; Other Information: PBD: 21 Feb 2000; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; URANIUM IODIDES; TETRAHYDROFURAN; PENTADIENES; CHEMICAL PREPARATION; LIGANDS; MOLECULAR STRUCTURE

Citation Formats

Avens, L R, Burns, C J, Butcher, R J, Clark, D L, Gordon, J C, Schake, A R, Scott, B L, Watkin, J G, and Zwick, B D. 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}. United States: N. p., 2000. Web. doi:10.1021/om990718r.
Avens, L R, Burns, C J, Butcher, R J, Clark, D L, Gordon, J C, Schake, A R, Scott, B L, Watkin, J G, & Zwick, B D. 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}. United States. doi:10.1021/om990718r.
Avens, L R, Burns, C J, Butcher, R J, Clark, D L, Gordon, J C, Schake, A R, Scott, B L, Watkin, J G, and Zwick, B D. Mon . "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}". United States. doi:10.1021/om990718r.
@article{osti_20017493,
title = {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}},
author = {Avens, L R and Burns, C J and Butcher, R J and Clark, D L and Gordon, J C and Schake, A R and Scott, B L and Watkin, J G and Zwick, B D},
abstractNote = {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.},
doi = {10.1021/om990718r},
journal = {Organometallics},
issn = {0276-7333},
number = 4,
volume = 19,
place = {United States},
year = {2000},
month = {2}
}