title: Experimental and Computational Studies on the Formation of Thorium-Copper Heterobimetallics.
abstract: The formation of actinide-transition metal heterobimetallics mediated by a terminal actinide imido complex was comprehensively studied. The reaction of the thorium imido complex [(η5-C5Me5)2Th=N(mesityl)(DMAP)] (3), prepared from [(η5-C5Me5)2ThMe2] (1) and mesitylNH2or [(η5-C5Me5)2Th(NHmesityl)2] (2) in the presence of 4-(dimethylamino)pyridine (DMAP), with copper(I) halides gave the first thorium-copper heterobimetallic compounds [(η5-C5Me5)2Th(X){N(mesityl)Cu(DMAP)}] (X=Cl (4), Br (5), I (6)). Complexes 4-6 feature an unusual geometry with a short Th-Cu distance, which DFT studies attribute to a weak donor-acceptor bond from the Cu+atom to the electropositive Th4+atom. They are reactive species, as was shown by their reaction with the dimethyl complex [(η5-C5Me5)2ThMe2] (1). Furthermore, a comparison between Th and early transition metals confirmed that Th4+exhibits distinctively different reactivity from d-transition metals.
authors.affiliation: Department of Chemistry, Beijing Normal University, Beijing, 100875, P.R. China.
authors.forename: Pikun
authors.initials: P
authors.lastname: Yang
authors.affiliation: Department of Chemistry, Beijing Normal University, Beijing, 100875, P.R. China.
authors.forename: Enwei
authors.initials: E
authors.lastname: Zhou
authors.affiliation: Department of Chemistry, Beijing Normal University, Beijing, 100875, P.R. China.
authors.forename: Guohua
authors.initials: G
authors.lastname: Hou
authors.affiliation: Department of Chemistry, Beijing Normal University, Beijing, 100875, P.R. China. gzi@bnu.edu.cn.
authors.forename: Guofu
authors.initials: G
authors.lastname: Zi
authors.affiliation: Department of Chemistry, Beijing Normal University, Beijing, 100875, P.R. China. dingwanjian@bnu.edu.cn.
authors.forename: Wanjian
authors.initials: W
authors.lastname: Ding
authors.affiliation: Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106, Braunschweig, Germany. mwalter@tu-bs.de.
authors.forename: Marc D
authors.initials: MD
authors.lastname: Walter
keywords: copper; heterometallic complexes; imido complexes; thorium; thorium-copper bond