A Step Too Far? Assessment of the Boroxide Ligand in Ring-Opening Polymerization

Cole, Sarah C, Coles, Martyn P and Hitchcock, Peter B (2004) A Step Too Far? Assessment of the Boroxide Ligand in Ring-Opening Polymerization. Organometallics, 23 (22). 5159 - 5168. ISSN 0276-7333

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Dimesityl borinic acid, (mes)2BOH [mes = 2,4,6-Me3C6H2], has been employed as a source of boroxide ligand in lithium, zinc, and magnesium chemistry; for structural comparisons, the alkoxide ligand [OCH(mes)2]- has also been used. The lithium compounds [Li{OB(mes)2}(L)n]2 [1a, L = Et2O, n = 1; 1b, L = Py, n = 1; 1c, L = MeCN, n = 2] have been structurally characterized, showing a common bimetallic core with bridging boroxide ligands that differ in the relative rotation of the "BC2" unit about the Li2O2 metallacycle. The zinc compounds [Zn{OR}Me]2 [2, R = B(mes)2; 3, R = CH(mes)2] have been synthesized from the reaction of ZnMe2 with the corresponding ROH species. As for the Li salts, 2 and 3 display a dimeric solid-state structure with -OR ligands. Reaction of the in situ generated lithium boroxide 1a with MgBrEt2O afforded an unprecedented tetrametallic compound, [Mg{OB(mes)2}BLiBr(OEt2)2]2 (4), in which the lithium bromide side product is retained in a tricyclic structure containing a "Li(-Br)2Mg{-OB(mes)2}Mg(-Br)2Li" core. The magnesium alkyl compounds [Mg{OB(mes)2}R(THF)]2 [5, R = Me; 6, R = Bu] were obtained from the reaction of the Li salt with the Grignard reagent, MgMeBr, and protonolysis of MgBu2 with (mes)2BOH, respectively. X-ray crystallography showed formation of a dimer in each case, where in 6 only the n-butyl group was observed in the solid state. Attempts at combining the boroxide ligand with the widely used -diketiminate ligand, [HC{C(Me)NAr}2]- (BDI), at a zinc center are discussed, and a brief study into the potential of selected zinc complexes to initiate the ring-opening polymerization of -caprolactone and rac-lactide is described.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Martyn Coles
Date Deposited: 06 Feb 2012 20:58
Last Modified: 19 Mar 2013 14:04
URI: http://sro.sussex.ac.uk/id/eprint/28951
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