Ehweiner, M. A., Belaj, F., Kirchner, K., & Mösch-Zanetti, N. C. (2021). Synthesis and Reactivity of a Bioinspired Molybdenum(IV) Acetylene Complex. Organometallics, 40(15), 2576–2583. https://doi.org/10.1021/acs.organomet.1c00289
E163-01-1 - Forschungsgruppe Organometallische Chemie und Katalyse
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Journal:
Organometallics
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ISSN:
0276-7333
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Date (published):
9-Aug-2021
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Number of Pages:
8
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Publisher:
AMER CHEMICAL SOC
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Peer reviewed:
Yes
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Keywords:
Inorganic Chemistry; Physical and Theoretical Chemistry; Organic Chemistry
en
Abstract:
The isolation of a molybdenum(IV) acetylene (C₂H₂) complex containing two bioinspired 6-methylpyridine-2-thiolate ligands is reported. The synthesis can be performed either by oxidation of a molybdenum(II) C₂H₂ complex or by substitution of a coordinated PMe₃ by C₂H₂ on a molybdenum(IV) center. Both C₂H₂ complexes were characterized by spectroscopic means as well as by single-crystal X-ray diffraction. Furthermore, the reactivity of the coordinated C₂H₂ was investigated with regard to acetylene hydratase, one of two enzymes that accept C₂H₂ as a substrate. While the reaction with water resulted in the vinylation of the pyridine-2-thiolate ligands, an intermolecular nucleophilic attack on the coordinated C₂H₂ with the soft nucleophile PMe₃ was observed to give a cationic ethenyl complex. A comparison with the tungsten analogues revealed less tightly bound C₂H₂ in the molybdenum variant, which, however, shows a higher reactivity toward nucleophiles.
