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Mixture of Azolium Tetraphenylborate with Isopropylthioxanthone: A New Class of N‐Heterocyclic Carbene (NHC) Photogenerator for Polyurethane, Polyester, and ROMP Polymers Synthesis
Author(s) -
Trinh Thi Kim Hoang,
Malval JeanPierre,
MorletSavary Fabrice,
Pinaud Julien,
LacroixDesmazes Patrick,
Reibel Corine,
Héroguez Valérie,
Chemtob Abraham
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901000
Subject(s) - carbene , tetraphenylborate , polymer chemistry , polymerization , chemistry , adduct , polyester , photochemistry , metathesis , polymer , catalysis , organic chemistry , ion
In the search of smarter routes to control the conditions of N‐heterocyclic carbene (NHCs) formation, a two‐component air‐stable NHC photogenerating system is reported. It relies on the irradiation at 365 nm of a mixture of 2‐isopropylthioxanthone (ITX) with 1,3‐bis(mesityl)imidazoli(ni)um tetraphenylborate. The photoinduced liberation of NHC is evidenced by reaction with a mesitoyl radical to form an NHC‐radical adduct detectable by electron spin resonance spectroscopy. The NHC yield can be determined by 1 H NMR spectroscopy through the formation of a soluble and stable NHC–carbodiimide adduct. To deprotonate the azolium salt and liberate the NHC, a mechanism is proposed in which the role of base is played by ITX radical anion formed in situ by a primary photoinduced electron‐transfer reaction between electronically excited ITX (oxidant) and BPh 4 − (reductant). An NHC yield as high as 70 % is achieved upon starting with a stoichiometric ratio of ITX and azolium salt. Three different photoNHC‐mediated polymerizations are described: synthesis of polyurethane and polyester by organocatalyzed step‐growth polymerization and ring‐opening copolymerization, respectively, and generation of polynorbornene by ring‐opening metathesis polymerization using an NHC‐coordinated Ru catalyst formed in situ.