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Synthesis and Reactivity of a Bioinspired Molybdenum(IV) Acetylene Complex.

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.

SUBMITTER: Ehweiner MA

PROVIDER: S-EPMC8356224 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature

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Synthesis and Reactivity of a Bioinspired Molybdenum(IV) Acetylene Complex.

Ehweiner Madeleine A MA Belaj Ferdinand F Kirchner Karl K Mösch-Zanetti Nadia C NC

Organometallics 20210705 15

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 diffract ...[more]

PMID: 34393319

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