Experimental and Computational Studies on the Formation of Thorium-Copper Heterobimetallics

摘要

The formation of actinide-transition metal heterobimetallics mediated by a terminal actinide imido complex was comprehensively studied. The reaction of the thorium imido complex [(eta(5)-C5Me5)(2)Th=N(mesityl)(DMAP)] (3), prepared from [(eta(5)-C5Me5)(2)ThMe2] (1) and mesitylNH(2) or [(eta(5)-C5Me5)(2)Th(NHmesityl)(2)] (2) in the presence of 4-(dimethylamino)pyridine (DMAP), with copper(I) halides gave the first thorium-copper heterobimetallic compounds [(eta(C5Me5)-C-5)(2)Th(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 [(eta(C5Me5)-C-5)(2)ThMe2] (1). Furthermore, a comparison between Th and early transition metals confirmed that Th4+ exhibits distinctively different reactivity from d-transition metals.