The Exceptional Diversity of Homoleptic Uranium–Methyl Complexes. (4th June 2020)

• Record Type: Journal Article
• Authors: Sears, Jeffrey D.; Sergentu, Dumitru‐Claudiu; Baker, Tessa M.; Brennessel, William W.; Autschbach, Jochen; Neidig, Michael L.
• Is Part Of: Angewandte Chemie. Volume 132:Number 32(2020)
• Page Start: 13688
• Page End: 13692
• Publication Date: 2020-06-04
• Subjects: homoleptic complexes -- organometallic compounds -- uranium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202005138
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Homoleptic σ‐bonded uranium–alkyl complexes have been a synthetic target since the Manhattan Project. The current study describes the synthesis and characterization of several unprecedented uranium–methyl complexes. Amongst these complexes, the first example of a homoleptic uranium–alkyl dimer, [Li(THF)4 ]2 [U2 (CH3 )10 ], as well as a seven‐coordinate uranium–methyl monomer, {Li(OEt2 )Li(OEt2 )2 UMe7 Li} n were both crystallographically identified. The diversity of complexes reported herein provides critical insight into the structural diversity, electronic structure and bonding in uranium–alkyl chemistry. Abstract : A diverse group of homoleptic uranium–methyl complexes is presented. The addition of MeLi to UCl4 at low temperature yields an unprecedented homoleptic uranium–methyl dimer. Overall this complex as well as several other monomeric uranium–alkyl complexes demonstrate the rich coordination and electronic structure and bonding of homoleptic uranium–alkyl complexes with sterically unencumbered alkyl substituents.