title: The nature of unsupported uranium-ruthenium bonds: a combined experimental and theoretical study.
abstract: Four new uranium-ruthenium complexes, [(Tren(TMS))URu(η(5)-C(5)H(5))(CO)(2)] (9), [(Tren(DMSB))URu(η(5)-C(5)H(5))(CO)(2)] (10), [(Ts(Tolyl))(THF)URu(η(5)-C(5)H(5))(CO)(2)] (11), and [(Ts(Xylyl))(THF)URu(η(5)-C(5)H(5))(CO)(2)] (12) [Tren(TMS)=N(CH(2)CH(2)NSiMe(3))(3); Tren(DMSB)=N(CH(2)CH(2)NSiMe(2)tBu)(3)]; Ts(Tolyl)=HC(SiMe(2)NC(6)H(4)-4-Me)(3); Ts(Xylyl)=HC(SiMe(2)NC(6)H(3)-3,5-Me(2))(3)], were prepared by a salt-elimination strategy. Structural, spectroscopic, and computational analyses of 9-12 shows: i) the formation of unsupported uranium-ruthenium bonds with no isocarbonyl linkages in the solid state; ii) ruthenium-carbonyl backbonding in the [Ru(η(5)-C(5)H(5))(CO)(2)](-) ions that is tempered by polarization of charge within the ruthenium fragments towards uranium; iii) closed-shell uranium-ruthenium interactions that can be classified as predominantly ionic with little covalent character. Comparison of the calculated U-Ru bond interaction energies (BIEs) of 9-12 with the BIE of [(η(5)-C(5)H(5))(3)URu(η(5)-C(5)H(5))(CO)(2)], for which an experimentally determined U-Ru bond disruption enthalpy (BDE) has been reported, suggests BDEs of approximately 150 kJ mol(-1) for 9-12.
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.forename: Dipti
authors.initials: D
authors.lastname: Patel
authors.forename: Andrew D
authors.initials: AD
authors.lastname: Cornish
authors.forename: Jonathan
authors.initials: J
authors.lastname: McMaster
authors.forename: William
authors.initials: W
authors.lastname: Lewis
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.forename: Stephen T
authors.initials: ST
authors.lastname: Liddle
mesh_terms: D018360:Crystallography, X-Ray; D008958:Models, Molecular; D008962:Models, Theoretical; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry; D014501:Uranium / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D014501:Uranium; D012428:Ruthenium