title: Synthesis and reactivity of uranium(IV) amide complexes supported by a triamidotriazacyclononane ligand.
abstract: Reaction of [U{(SiMe2NPh)3-tacn}Cl] with LiNEt2 or LiNPh2 affords the corresponding amide compounds, [U{(SiMe2NPh)3-tacn}(NR2)] (R = Et (1), R = Ph (2)). The complexes have been fully characterized by spectroscopic methods and the solid-state structure of 1 was determined by single-crystal X-ray diffraction analysis. The six nitrogen atoms of the tris(dimethylsilylanilide)triazacyclononane ligand are in a trigonal prismatic configuration with the nitrogen atom of the diethylamide ligand capping one of the trigonal faces of the trigonal prism. Crystallization of 2 from CH3CN solution gave crystals of the six-membered heterocycle [U{(SiMe2NPh)3-tacn}{kappa2-(HNC(Me))2CC[triple bond]N}] (3). The reactivity of the amides was investigated. Both compounds undergo acid-base reactions with protic substrates such as HOC6H2-2,4,6-Me3, 3,5-Me2pzH (pz = pyrazolyl) and HSC5H4N to give the corresponding [U{(SiMe2NPh)3-tacn}X] (X = OC6H2-2,4,6-Me3 (4), 3,5-Me2pzH (5), kappa2-SC5H4N (6)) complexes. The solid-state structures of and were determined by single-crystal X-ray diffraction and revealed that the compounds are eight-coordinate with dodecahedral geometry.
authors.affiliation: Departamento de Química, ITN, Estrada Nacional 10, P-2686-953, Sacavém, Portugal.
authors.forename: Maria Augusta
authors.initials: MA
authors.lastname: Antunes
authors.forename: Marta
authors.initials: M
authors.lastname: Dias
authors.forename: Bernardo
authors.initials: B
authors.lastname: Monteiro
authors.forename: Angela
authors.initials: A
authors.lastname: Domingos
authors.forename: Isabel C
authors.initials: IC
authors.lastname: Santos
authors.forename: Noémia
authors.initials: N
authors.lastname: Marques