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

Supplementary Information files for Insights into the structures adopted by titanocalix[6 and 8]arenes and their use in the ring opening polymerization of cyclic estersInteraction of p-tert-butylcalix[6]areneH6, L1
H6, 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.

补充信息文件，揭示了钛卡利克[6和8]芳烃的结构及其在环状酯开环聚合中的应用。p-叔丁基卡利克[6]芳烃H6、L1H6与[TiCl4]的反应生成了配合物[Ti2Cl3(MeCN)2(OH2)(L1H)][Ti2Cl3(MeCN)3(L1H)]·4.5MeCN (1·4.5MeCN)，其中两个假八面体钛中心与一个卡利克[6]芳烃结合。采用四氢呋喃（THF）进行的类似反应产生了THF开环产物[Ti4Cl2(μ3-O)2(NCMe)2(L)2(O(CH2)4Cl)2]·4MeCN (2·4MeCN)，其中LH4为p-叔丁基卡利克[4]芳烃H4。L1H6与TiF4 (3 equiv.)反应，经过处理得到配合物[(TiF)2(μ-F)L1H]2·6.5MeCN (3·6.5MeCN)。p-叔丁基卡利克[8]芳烃H8、L2H8与[TiCl4]的反应导致了配合物[(TiCl)2(TiClNCMe)2(μ3-O)2(L2)]·1.5MeCN (4·1.5MeCN)的分离。类似的反应产生了共晶配合物[Ti4O2Cl4(MeCN)2(L2)][Ti3Cl6(MeCN)5(OH2)(L2H2)]·H2O·11MeCN (5·H2O 11MeCN)。将L2H8的化学扩展到[TiBr4]，根据化学计量比，产生了配合物[(TiBr)2(TiBrNCMe)2(μ3-O)2(L2)]·6MeCN (6·6MeCN)或[Ti(NCMe)2Br]2[Ti(O)Br2(NCMe)](L2)]·7.5MeCN (7·7.5MeCN)，而使用[TiF4]产生了含有Ca2+和Na+的配合物，据推测这些阳离子来源于干燥剂，即[Ti8CaF20(OH2)Na2(MeCN)4(L2)2]·14MeCN (8·14MeCN)、[Na(MeCN)2][Ti8CaF20NaO16(L2)2]·7MeCN (9·7MeCN)或[Na]6[Ti8F20Na(MeCN)2(L2)][Ti8F20Na(MeCN)0.5(L2)]·15.5(C2H3N) (10·15.5MeCN)。在TiI4的情况下，分离出了梯形配合物[(TiI)2(TiINCMe)2(μ3-O)2(L2)]·7.25CH2Cl2 (11·7.25CH2Cl2)。这些配合物已筛选其作为环状开环聚合（ROP）催化剂的潜力，聚合对象为ε-己内酯（ε-CL）、δ-戊内酯（δ-VL）和rac-乳酸（r-LA），反应均在空气和氮气中进行。对于ε-CL和δ-VL，1、9和11在130°C下24小时内的活性适中；对于r-LA，只有1表现出合理的活性。在ε-CL与δ-VL的共聚合中，1和11提供了合理的转化率和低分子量聚合物，而4、6和9的效果较差。在所采用的条件下，没有配合物在ε-CL与r-LA的共聚合中表现出活性。