Molybdenum and Tungsten Imido Alkylidene N-Heterocyclic Carbene Catalysts Bearing Cationic Ligands for Use in Biphasic Olefin Metathesis.

Title Molybdenum and Tungsten Imido Alkylidene N-Heterocyclic Carbene Catalysts Bearing Cationic Ligands for Use in Biphasic Olefin Metathesis.
Authors I. Elser; R. Schowner; W. Frey; M.Rudolf Buchmeiser
Journal Chemistry
DOI 10.1002/chem.201700213
Abstract

Ionic Mo- and W-imido alkylidene N-heterocyclic carbene (NHC) olefin metathesis catalysts, [Mo(N-2,6-Me2-C6H3)(CHCMe2Ph)(IMesH2)(OTf)(PPS)][OTf] (3), [Mo(N-2,6-Me2-C6H3)(CHCMe2Ph)(IMesH2)(OC6F5)(PPS)][B(ArF)4] (5), [Mo(N-tBu)(CHCMe2Ph)(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)(OTf)(2,6-Ph-4-(2,4,6-Ph-pyridinium)phenolate)][OTf] (9), [Mo(N-tBu)(CHCMe2Ph)(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)(2,6-Ph-4-(2,4,6-Ph-pyridinium)phenolate)][B(ArF)4]2 (10, PPS = pyridiniumpropanesulfonate, IMesH2 = 1,3-dimesitylimidazolin-2-ylidene, OTf = CF3SO3, B(ArF)4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) were prepared from betaine-type ligands. Also, the first bis-NHC and a nitron-based bis(amido) bistriflate imido alkylidene complex, [Mo(N-tBu)(CHCMe2Ph)(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)2(THF)(2,6-Ph-4-(2,4,6-Ph-pyridinium)phenolate)][OTf]2 (11) and [Mo(N-2,6-Me2-C6H3)(CHCMe2Ph)(N-(1,4-diphenyl-1,3,4-triazol-2-ylium)-N-phenyl-amido)2][OTf]2 (14) along with ionic W(N-2,6-iPr2-C6H3)(CHCMe2Ph)(N-2,5-Me2C4H2)(IPr)(2,6-tBu-4-PPh3-phenolate) are reported. With these new catalysts, the first biphasic reaction setup with group 6 metal alkylidene NHC complexes was successfully established using pyrrole / heptane as liquid phases. Productivities under biphasic conditions were comparable to those of reactions in 1,2-dichloroethane or toluene. < 2 ppm of metals migrated into the nonpolar heptane phase as measured by inductively coupled plasma-optical emission spectroscopy.

Citation I. Elser; R. Schowner; W. Frey; M.Rudolf Buchmeiser.Molybdenum and Tungsten Imido Alkylidene N-Heterocyclic Carbene Catalysts Bearing Cationic Ligands for Use in Biphasic Olefin Metathesis.. Chemistry. 2017. doi:10.1002/chem.201700213

Related Elements

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Molybdenum

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