Experimental and Computational Studies on the Formation of Thorium–Copper Heterobimetallics |
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| Authors: | Pikun Yang Enwei Zhou Dr. Guohua Hou Prof. Guofu Zi Dr. Wanjian Ding Dr. Marc D. Walter |
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| Affiliation: | 1. Department of Chemistry, Beijing Normal University, Beijing, P.R. China;2. Institut für Anorganische und Analytische Chemie, Technische Universit?t Braunschweig, Braunschweig, Germany |
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| 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 mesitylNH2 or [(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. |
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| Keywords: | copper heterometallic complexes imido complexes thorium thorium– copper bond |
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