Organomolybdenum (VI) and lithium Organomolybdate (VI) and (V) Complexes with C,N-Chelating Aminoaryl Ligands

Abstract

The synthesis and characterization of new, five-coordinate molybdenum bis(imidoaryl) complexes [Mo(NAr)2(C-N)X] (Ar = C6H3i-Pr2-2,6; C-N = [C6H4(CH2NMe2)-2]-; X = Cl (1), Me (2), Et (3), Bu (4), CH2SiMe3 (5), (p-tolyl) (6), (C-N) (7)) is reported. The solid-state structure of 2 has been elucidated by single-crystal X-ray analysis. Compounds 2, 3, 4, 5, and 6 react with alkyl- or aryllithium compounds to form lithium molybdate(VI) derivatives, of which [Li(DME)Mo(NAr)2(C-N)(Me)(p-tolyl)] (10), formed by the reaction of 2 with [Li(p-tolyl)], has been structurally (X-ray) characterized. Thermal activation of these lithium molybdates leads to the formation of paramagnetic lithium molybdate(V) compounds instead of the anticipated molybdenum(VI) alkylidenes. The actual temperature (between -10 and 80 C) at which paramagnetic Mo(V) radical anions are formed is dependent on both the type of alkyl or aryl substituent (introduced via LiR') and the solvent. The synthesis of [LiMo(NAr)2(C-N)2] (11) by reaction of 7 with n-BuLi is described. The initially formed lithium molybdate(VI) compound [Li(DME)nMo(NAr)2(C-N)2(n-Bu)] is not stable at room temperature and converts directly to the lithium molybdate(V) derivative 11. The solid-state structure of 11 has been elucidated by single-crystal X-ray analysis. None of the lithium molybdate(VI) nor -(V) derivatives described herein are active catalysts for ROMP, as thermal activation does not lead to the formation of a molybdenum alkylidene complex but to electron transfer and formation of a lithium molybdate(V) instead. However, upon treatment of a solution of any of the molybdate(V) derivatives with dry air, catalytic ROMP is observed.