title: Triamidoamine uranium(IV)-arsenic complexes containing one-, two- and threefold U-As bonding interactions.
abstract: To further our fundamental understanding of the nature and extent of covalency in uranium-ligand bonding, and the benefits that this may have for the design of new ligands for nuclear waste separation, there is burgeoning interest in the nature of uranium complexes with soft- and multiple-bond-donor ligands. Despite this, there have so far been no examples of structurally authenticated molecular uranium-arsenic bonds under ambient conditions. Here, we report molecular uranium(IV)-arsenic complexes featuring formal single, double and triple U-As bonding interactions. Compound formulations are supported by a range of characterization techniques, and theoretical calculations suggest the presence of polarized covalent one-, two- and threefold bonding interactions between uranium and arsenic in parent arsenide [U-AsH2], terminal arsinidene [U=AsH] and arsenido [U≡AsK2] complexes, respectively. These studies inform our understanding of the bonding of actinides with soft donor ligands and may be of use in future ligand design in this area.
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
authors.forename: Benedict M
authors.initials: BM
authors.lastname: Gardner
authors.affiliation: Institut of Inorganic Chemistry, University of Regensburg, Universitaets Strasse 31, Regensburg 93053, Germany.
authors.forename: Gábor
authors.initials: G
authors.lastname: Balázs
authors.affiliation: Institut of Inorganic Chemistry, University of Regensburg, Universitaets Strasse 31, Regensburg 93053, Germany.
authors.forename: Manfred
authors.initials: M
authors.lastname: Scheer
authors.affiliation: School of Chemistry and Photon Science Institute, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Floriana
authors.initials: F
authors.lastname: Tuna
authors.affiliation: School of Chemistry and Photon Science Institute, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Eric J L
authors.initials: EJ
authors.lastname: McInnes
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
authors.forename: Jonathan
authors.initials: J
authors.lastname: McMaster
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
authors.forename: William
authors.initials: W
authors.lastname: Lewis
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
authors.forename: Alexander J
authors.identifier: 0000000322578332
authors.initials: AJ
authors.lastname: Blake
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
authors.forename: Stephen T
authors.initials: ST
authors.lastname: Liddle