Well-defined Ti4 pre-catalysts for the ring-opening polymerisation of lactide

Cols, Jean-Marie E.  P.; Taylor, Cameron E.; Gagnon, Kevin J.; Teat, Simon J.; McIntosh, Ruaraidh D.

doi:10.1039/c6dt03842e

Title: Well-defined Ti₄ pre-catalysts for the ring-opening polymerisation of lactide

Journal Article · Mon Oct 17 00:00:00 EDT 2016 · Dalton Transactions

DOI:https://doi.org/10.1039/c6dt03842e· OSTI ID:1439189

Cols, Jean-Marie E. P. ^[1]; Taylor, Cameron E. ^[1]; Gagnon, Kevin J. ^[2]; Teat, Simon J. ^[2];

^[1]

Heriot-Watt Univ., Edinburgh, Scotland (United Kingdom). Inst. of Chemical Sciences
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Here, the synthesis and full characterisation of four discrete tetrametallic titanium complexes is reported. These well-defined compounds are isostructural in the solid state and share the same general formula: Ti₄(μ-O)₂L₄ (L = 1, 2, 3 or 4). Using a combination of NMR techniques the complexes are found to be stable in solution, even at elevated temperatures. Further studies show that the carboxylate moieties of the supporting amine bis(phenolate) ligands can be displaced by a more strongly coordinating solvent. This reversible process causes the coordinatively saturated Ti₄(μ-O)₂L₄ complexes to separate into two Ti₂(μ-O)L₂ subunits which we envisaged would be catalytically active. Proof-of-concept experiments establish that all four of these complexes display catalytic activity in the ring-opening polymerisation of rac-lactide. These aggregates can therefore be viewed as air and moisture stable pre-catalysts for a range of reactions.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Heriot-Watt Univ., Edinburgh, Scotland (United Kingdom); Swansea Univ., Wales (United Kingdom)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1439189

Journal Information:: Dalton Transactions, Vol. 45, Issue 44; Related Information: © 2016 The Royal Society of Chemistry.; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 8 works

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CCDC 1483652: Experimental Crystal Structure Determination: OYIFAF : tetrakis(μ-N,N-bis(2-oxybenzyl)glycinato)-bis(μ-oxo)-tetra-titanium acetonitrile unknown solvate Cols, Jean-Marie; Taylor, Cameron; Gagnon, Kevin https://doi.org/10.5517/ccdc.csd.cc1lsvrz The current record is supplemented by this dataset	dataset	June 2016
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Title: Well-defined Ti4 pre-catalysts for the ring-opening polymerisation of lactide

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