Thorium 2-pyridylamidinates: synthesis, structure and catalytic activity towards the cyclo-oligomerization of ε-caprolactone

Abstract

Salt metathesis of ThCl(4).3THF with N,N'-bis(trimethylsilyl)-2-pyridyl-lithium-TMEDA (1) yields bis(N,N'-bis(trimethylsilyl)-2-pyridylamidinate) thorium-chloride (mu-Cl)(2)Li(TMEDA) (2) (60% isolated yield) and tris(N,N'-bis(trimethylsilyl)-2-pyridylamidinate) thorium monochloride (3) (10% isolated yield). The latter compound is the first crystallographically characterized tris(amidinate) thorium complex. The bis pyridyl amidinate thorium (2) displays a unique reactivity towards the dual-site cyclo-oligomerization of epsilon-caprolactone, which produces two fractions of macrocyclic oligo-esters with extremely narrow (1.01-1.06) polydispersity. A mechanism for the dual-site oligomerization reaction is proposed based on kinetic, poisoning, and (1)H NMR studies.