This is a comprehensive study of the effects of rationally designed hemilabile ligands on the stability, reactivity, and change in catalytic behavior of indium complexes. We report cationic alkyl indium complexes supported by a family of hemi-salen type ligands bearing hemilabile thiophenyl (2a), furfuryl (2b) and pyridyl (2c) pendant donor arms. Shelf-life and stability of these complexes followed the trend 2a<2b<2c, showing direct correlation to the affinity of the pendant donor group to the indium center. Reactivity towards polymerization of epichlorohydrin and cyclohexene oxide followed the trend 2a>2b>2c with control of polymerization following an inverse relationship to reactivity. Surprisingly, 2c polymerized racemic lactide without an external initiator, likely through an alkyl-initiated coordination-insertion mechanism.
Publications
(59) Phys. Fluids 2021, 33, 043102
(58) Phys. Fluids 2021, 33, 032010
(57) Polym. Chem. 2021, 12, 783 - 806
(56) Catal. Sci. Technol. 2021, 11, 2119–2129
(55) Catal. Sci. Technol. 2021, 11, 62-91
(54) ACS Appl. Mater. Interfaces 2020, 12, 52182−52191
(53) Macromolecules 2020, 53(20), 8819-8828
(52) ACS Catal. 2020, 10, 6488−6496
(51) Chem. Sci. 2020, 11, 6485−6491
(50) Inorg. Chem. 2020, 59, 5546−5557
(49) Chem. Commun. 2019, 55, 3347-3350
(48) Coord. Chem. Rev. 2019 380, 35–57
(47) ChemCatChem 2018, 10, 3219 – 3222
(46) ACS Sustainable Chem. Eng., 2018, 6, 1650–1661
(45) Acc. Chem. Res. 2017, 50, 2861−2869
(44) J. Rheol. 2017 61(6), 1137-1148
(43) ACS Catal. 2017, 7, 6413−6418
(42) Dalton Trans. 2017 46, 6723–6733
(41) Macromolecules 2017 50 (6), 2535–2546
(40) Inorg. Chem. 2017 56 (3), 1375–1385
(39) Macromolecules 2016 49 (23), 8812–8824
(38) Inorg. Chem. 2016, 55(18), 9445–9453
(37) Inorg. Chem. 2016, 55(11), 5365–5374
(36) Macromolecules 2016, 49(3), 909–919
(35) Macromolecules 2015, 48(18), 6672-6681
(34) Chem. Sci., 2015, 6, 5284–5292
(33) Dalton Trans. 2015, 44, 14248 - 14254
(32) Dalton Trans. 2015, 44, 6126 - 6139
(31) Inorg. Chem. 2014, 53(18), 9897−9906
(30) J. Am. Chem. Soc. 2014, 136(32), 11264–11267
(29) Inorg. Chem. 2014, 53(13), 6828–6836
(28) Organometallics 2013, 32(23), 6950–6956
(27) Macromolecules 2013, 46, 3965−3974
(26) Chem. Commun. 2013, 49, 4295-4297
(25) J. Am. Chem. Soc. 2012, 134(30), 12758–12773
(24) Chem. Commun. 2012, 48(54), 6806-6808
(23) Polymer 2012, 53(12), 2443-2452
(22) Dalton Trans. 2012, 41(26), 8123-8134.
(21) Rheol. Acta 2012, 51(4), 357-369
(20) J. Am. Chem. Soc. 2011, 133(24), 9278–9281
(19) J. Rheol. 2011, 55(5), 987-1004
(18) Organometallics 2010, 29(22), 6065–6076
(17) Inorg. Chem. 2010, 49(12), 5444–5452
(16) Dalton Trans. 2010, 39(2), 541–547
(15) J. Supercrit. Fluids 2010, 51(3), 376-383
(14) Organometallics 2009, 28(21), 6370–6373
(13) Organometallics 2009, 28(13), 3889–3895
(12) Organometallics, 2009, 28(5), 1309-1319
(11) Angew. Chem. Int. Ed. 2008, 47(12), 2290-2293