Neodymium borohydride complexes supported by diamino-bis(phenoxide) ligands: diversity of synthetic and structural chemistry, and catalytic activity in ring-opening polymerization of cyclic esters

Kerton, Francesca M. and Sinenkov, Mikhail A. and Fukin, Georgy K. and Cherkasov, Anton V. and Ajellal, Noureddine and Roisnel, Thierry and Carpentier, Jean-François and Trifonov, Alexander A. (2010) Neodymium borohydride complexes supported by diamino-bis(phenoxide) ligands: diversity of synthetic and structural chemistry, and catalytic activity in ring-opening polymerization of cyclic esters. New Journal of Chemistry, 35 (1). pp. 204-212. ISSN 1369-9261

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Abstract

New heterobimetallic borohydrido neodymium complexes {[OONN]1Nd(BH4)(m-BH4)Li(THF)}2 (1) and [OONN]3Nd(BH4)(m-BH4)Li(THF)2 (3) supported by diamino-bis(phenoxide) ligands ([OONN]1 = {CH2N(Me)CH2-3,5-Me,t-Bu-C6H2O}2; [OONN]3 = C5H4NCH2N-{CH2-3,5-Me,t-Bu-C6H2O}2) were synthesized by the reactions of Nd(BH4)3(THF)2 with equimolar amounts of dilithium derivatives of diamino-bis(phenol)s Li2[OONN]n and isolated in high yields. In the case of Li2[OONN]2 ([OONN]2=Me2NCH2CH2N{CH2-3,5-t-Bu-C6H2O}2), the same synthetic procedure afforded the heterobimetallic bis(phenoxide) complex Li{Nd[OONN2]2} (2). The structures of complexes 1–3 were established by X-ray diffraction studies. Compounds 1–3 act as single-site initiators for the ring-opening polymerization (ROP) of racemic lactide and racemic b-butyrolactone under mild conditions (20 1C), providing atactic polymers with controlled molecular weights and relatively narrow polydispersities (Mw/Mn = 1.07–1.82). While 1 and 3 initiate polymerization via their borohydride groups, ROP with 2 proceeds via insertion into the Nd–O(ligand) bond.

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