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Insights into the structures adopted by titanocalix[6 and 8]arenes and their use in the ring opening polymerization of cyclic esters

Santoro, Orlando; Elsegood, Mark Robert James; Bedwell, Elizabeth; Pryce, Jake; Redshaw, Carl


Orlando Santoro

Mark Robert James Elsegood

Elizabeth Bedwell

Jake Pryce

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Professor Carl Redshaw
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry


Interaction of p-tert-butylcalix[6]areneH6, L1H6, with [TiCl4] afforded the complex [Ti2Cl3(MeCN)2(OH2)(L1H)][Ti2Cl3(MeCN)3(L1H)]∙4.5MeCN (1∙4.5MeCN), in which two pseudo octahedral titanium centres are bound to one calix[6]arene. A similar reaction but employing THF resulted in the THF ring-opened product [Ti4Cl2(μ3-O)2(NCMe)2(L)2(O(CH2)4Cl)2]∙4MeCN (2∙4MeCN), where LH4 = p-tert-butylcalix[4]areneH4. Interaction of L1H6 with TiF4 (3 equiv.) led, after work-up, to the complex [(TiF)2(μ -F)L1H]2∙6.5MeCN (3∙6.5MeCN). Treatment of p-tert-butylcalix[8]areneH8, L2H8, with [TiCl4] led to the isolation of the complex [(TiCl)2(TiClNCMe)2(μ3-O)2(L2)]∙1.5MeCN (4∙1.5MeCN). From a similar reaction, a co-crystallized complex [Ti4O2Cl4(MeCN)2(L2)][Ti3Cl6(MeCN)5(OH2)(L2H2)]·H2O∙11MeCN (5·H2O 11MeCN) was isolated. Extension of the L2H8 chemistry to [TiBr4] afforded, depending on the stoichiometry, the complexes [(TiBr)2(TiBrNCMe)2(μ3-O)2(L2)]∙6MeCN (6∙6MeCN) or [Ti(NCMe)2Br]2[Ti(O)Br2(NCMe)](L2)]∙7.5MeCN (7∙7.5MeCN), whilst use of [TiF4] afforded complexes containing Ca2+ and Na+, thought to originate from drying agents, namely [Ti8CaF20(OH2)Na2(MeCN)4(L2)2]∙14MeCN (8∙14MeCN), [Na(MeCN)2][Ti8CaF20NaO16(L2)2]∙7MeCN (9∙7MeCN) or [Na]6[Ti8F20Na(MeCN)2(L2)][Ti8F20Na(MeCN)0.5(L2)]∙15.5(C2H3N) (10∙15.5MeCN). In the case of TiI4, the ladder [(TiI)2(TiINCMe)2(μ3-O)2(L2)]∙7.25CH2Cl2 (11∙7.25CH2Cl2) was isolated. These complexes have been screened for their potential to act as catalysts in the ring opening polymerization (ROP) of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL) and rac-lactide (r-LA), both in air and N2. For ε-CL and δ-VL, moderate activity at 130 oC over 24 h was observed for 1, 9 and 11; for r-LA, only 1 exhibited reasonable activity. In the case of the co-polymerization of ε-CL with δ-VL, the complexes 1 and 11 afforded reasonable conversions and low molecular weight polymers, whilst 4, 6, and 9 were less effective. None of the complexes proved to be active in the co-polymerization of ε-CL and r-LA under the conditions employed herein.


Santoro, O., Elsegood, M. R. J., Bedwell, E., Pryce, J., & Redshaw, C. (2020). Insights into the structures adopted by titanocalix[6 and 8]arenes and their use in the ring opening polymerization of cyclic esters. Dalton transactions : an international journal of inorganic chemistry / RSoC, 49(34), 11978-11996.

Journal Article Type Article
Acceptance Date Aug 7, 2020
Online Publication Date Aug 10, 2020
Publication Date Sep 14, 2020
Deposit Date Aug 10, 2020
Publicly Available Date Aug 10, 2020
Journal Dalton Transactions
Print ISSN 1477-9226
Electronic ISSN 1477-9234
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 49
Issue 34
Pages 11978-11996
Keywords Inorganic Chemistry
Public URL
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