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Title: Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N -Heterocyclic Carbenes

Abstract

In this work, 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.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3]; ORCiD logo [4];  [1]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Stuttgart (Germany). Inst. of Polymer Chemistry
  2. Univ. of Stuttgart (Germany). Inst. of Organic Chemistry
  3. Univ. of Innsbruck (Austria). Inst. of General, Inorganic and Theoretical Chemistry
  4. Univ. of Stuttgart (Germany). Inst. for Theoretical Chemistry
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); German Research Foundation (DFG)
OSTI Identifier:
1598275
Grant/Contract Number:  
AC02-76SF00515; 358283783-CRC 1333
Resource Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 38; Journal Issue: 21; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Chemical structure; Metals; Ligands; Particulate matter; Crystal structure

Citation Formats

Elser, Iris, Groos, Jonas, Hauser, Philipp M., Koy, Maximilian, van der Ende, Melita, Wang, Dongren, Frey, Wolfgang, Wurst, Klaus, Meisner, Jan, Ziegler, Felix, Kästner, Johannes, and Buchmeiser, Michael R. Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N -Heterocyclic Carbenes. United States: N. p., 2019. Web. doi:10.1021/acs.organomet.9b00481.
Elser, Iris, Groos, Jonas, Hauser, Philipp M., Koy, Maximilian, van der Ende, Melita, Wang, Dongren, Frey, Wolfgang, Wurst, Klaus, Meisner, Jan, Ziegler, Felix, Kästner, Johannes, & Buchmeiser, Michael R. Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N -Heterocyclic Carbenes. United States. https://doi.org/10.1021/acs.organomet.9b00481
Elser, Iris, Groos, Jonas, Hauser, Philipp M., Koy, Maximilian, van der Ende, Melita, Wang, Dongren, Frey, Wolfgang, Wurst, Klaus, Meisner, Jan, Ziegler, Felix, Kästner, Johannes, and Buchmeiser, Michael R. Fri . "Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N -Heterocyclic Carbenes". United States. https://doi.org/10.1021/acs.organomet.9b00481. https://www.osti.gov/servlets/purl/1598275.
@article{osti_1598275,
title = {Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N -Heterocyclic Carbenes},
author = {Elser, Iris and Groos, Jonas and Hauser, Philipp M. and Koy, Maximilian and van der Ende, Melita and Wang, Dongren and Frey, Wolfgang and Wurst, Klaus and Meisner, Jan and Ziegler, Felix and Kästner, Johannes and Buchmeiser, Michael R.},
abstractNote = {In this work, 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.},
doi = {10.1021/acs.organomet.9b00481},
journal = {Organometallics},
number = 21,
volume = 38,
place = {United States},
year = {2019},
month = {10}
}

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Cited by: 21 works
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Figures / Tables:

Figure 1 Figure 1: Well-defined alkyne metathesis catalysts developed in the groups of Mortreux,6 Schrock,3a - i Cummins,7 Fiirstner,4a - d Moore,8 Tammsb- e and Buchmeiser.12

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