Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N-Heterocyclic Carbenes
- Iris ElserIris ElserInstitute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Iris Elser
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- Jonas GroosJonas GroosInstitute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Jonas Groos
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- Philipp M. HauserPhilipp M. HauserInstitute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Philipp M. Hauser
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- Maximilian KoyMaximilian KoyInstitute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Maximilian Koy
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- Melita van der EndeMelita van der EndeInstitute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Melita van der Ende
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- Dongren WangDongren WangInstitute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Dongren Wang
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- Wolfgang FreyWolfgang FreyInstitute of Organic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Wolfgang Frey
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- Klaus WurstKlaus WurstInstitute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, A-6020 Innsbruck, AustriaMore by Klaus Wurst
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- Jan MeisnerJan MeisnerInstitute for Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Jan Meisner
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- Felix ZieglerFelix ZieglerInstitute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Felix Ziegler
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- Johannes KästnerJohannes KästnerInstitute for Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Johannes Kästner
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- Michael R. Buchmeiser*Michael R. Buchmeiser*(M.R.B.): [email protected]Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyMore by Michael R. Buchmeiser
Abstract
New tungsten and molybdenum alkylidyne complexes bearing mono-, bi-, and tridentate N-heterocyclic carbenes (NHCs) have been synthesized. Formation of unprecedented structures in complexes bearing N-tert-butyl substituents on the imidazol(in)-2-ylidene was observed, leading to molybdenum complexes containing an abnormal carbene (Mo-4) and a bridging O,C,C-pincer ligand (Mo-10) and to a tungsten complex containing a cationic imidazolinium-tagged alkoxide forming an inner salt with an anionic tungsten center (W-5). Both the abnormal carbene binding in Mo-4 and the O,C,C-pincer-type structure of Mo-10 were confirmed by single-crystal X-ray analysis, and the proposed structure of W-5 is supported by the single-crystal X-ray structure of a minor byproduct (W-8) formed during the synthesis of W-4, displaying the aforementioned inner-salt-like structure. The novel alkylidyne complexes were also investigated for their capability to form a previously postulated quasi-cationic species with a weakly coordinating anion (WCA) during the alkyne homometathesis of 1-phenyl-1-propyne. Overall, incorporation of bidentate and strongly σ donating NHCs as well as introduction of better leaving groups did not lead to the expected increase in catalytic activity. Despite identical ligand spheres, changing from molybdenum to tungsten led to complete loss of activity in the bidentate systems.
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