Reactivity of the cationic uranium amide compound [U(η-C5Me5)2(NMe2)(OC4H8)][BPh4]

The cationic uranium amide compound [U(Cp*)(2)(NMe2)(THF)][BPh4] 1 (Cp* = eta-C5Me5, THF = tetrahydrofuran) was transformed into the heterocyclic metallacycle [(Cp*)(2)U(O(CH2)(4)NMe2(CH2)(4)O)][BPh4] .O5THF 2 in the presence of a catalytic amount of the free amine NR2H (R = Me, Et). Treatment of 1 with (BuNC)-Bu-t afforded the isocyanide adduct [U(Cp*)(2)(NMe2)((CNBu)-Bu-t)(2)][BPh4] 4 whereas reactions with MeCN, CO2 and CO gave the insertion compounds [U(Cp*)(2)(NC{Me}{NMe2})(THF)][BPh4] 5, [U(Cp*)(2)(O2CNMe2)(THF)][BPh4] 6 and [U(Cp*)(2)(eta(2)-CONMe2)(THF)][BPh4] 7. The crystal structure of a THF solvate of 4 has been determined. (C) 1997 Elsevier Science S.A. (C) 1997 Elsevier Science S.A.