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Structural Mimics of Acetylene Hydratase: Tungsten Complexes Capable of Intramolecular Nucleophilic Attack on Acetylene.
Chemistry 2019C

Abstract

Bioinspired complexes employing the ligands 6-tert-butylpyridazine-3-thione (SPn) and pyridine-2-thione (SPy) were synthesized and fully characterized to mimic the tungstoenzyme acetylene hydratase (AH). The complexes [W(CO)(C2 H2)(CHCH-SPy)(SPy)] (4) and [W(CO)(C2 H2)(CHCH-SPn)(SPn)] (5) were formed by intramolecular nucleophilic attack of the nitrogen donors of the ligand on the coordinated C2 H2 molecule. Labelling experiments using C2 D2 with the SPy system revealed the insertion reaction proceeding via a bis-acetylene intermediate. The starting complex [W(CO)(C2 H2)(SPy)2 ] (6) for these studies was accessed by the new acetylene precursor mixture [W(CO)(C2 H2)n (MeCN)3-n Br2 ] (n=1 and 2; 7). All complexes represent rare examples in the field of W-C2 H2 chemistry with 4 and 5 being the first of their kind. In the ongoing debate on the enzymatic mechanism, the findings support activation of acetylene by the tungsten center.

Authors+Show Affiliations

Institute of Chemistry-Inorganic Chemistry, University of Graz, Schubertstrasse 1, 8010, Graz, Austria.Institute of Chemistry-Inorganic Chemistry, University of Graz, Schubertstrasse 1, 8010, Graz, Austria.Institute of Chemistry-Inorganic Chemistry, University of Graz, Schubertstrasse 1, 8010, Graz, Austria.Institute of Chemistry-Inorganic Chemistry, University of Graz, Schubertstrasse 1, 8010, Graz, Austria.Institute of Chemistry-Inorganic Chemistry, University of Graz, Schubertstrasse 1, 8010, Graz, Austria.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31603595

Citation

Vidovič, Carina, et al. "Structural Mimics of Acetylene Hydratase: Tungsten Complexes Capable of Intramolecular Nucleophilic Attack On Acetylene." Chemistry (Weinheim an Der Bergstrasse, Germany), 2019.
Vidovič C, Peschel LM, Buchsteiner M, et al. Structural Mimics of Acetylene Hydratase: Tungsten Complexes Capable of Intramolecular Nucleophilic Attack on Acetylene. Chemistry. 2019.
Vidovič, C., Peschel, L. M., Buchsteiner, M., Belaj, F., & Mösch-Zanetti, N. C. (2019). Structural Mimics of Acetylene Hydratase: Tungsten Complexes Capable of Intramolecular Nucleophilic Attack on Acetylene. Chemistry (Weinheim an Der Bergstrasse, Germany), doi:10.1002/chem.201903264.
Vidovič C, et al. Structural Mimics of Acetylene Hydratase: Tungsten Complexes Capable of Intramolecular Nucleophilic Attack On Acetylene. Chemistry. 2019 Oct 11; PubMed PMID: 31603595.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Structural Mimics of Acetylene Hydratase: Tungsten Complexes Capable of Intramolecular Nucleophilic Attack on Acetylene. AU - Vidovič,Carina, AU - Peschel,Lydia M, AU - Buchsteiner,Michael, AU - Belaj,Ferdinand, AU - Mösch-Zanetti,Nadia C, Y1 - 2019/10/11/ PY - 2019/07/17/received PY - 2019/10/12/entrez KW - acetylene hydratases KW - acetylene ligands KW - bioinorganic chemistry KW - tungsten JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry N2 - Bioinspired complexes employing the ligands 6-tert-butylpyridazine-3-thione (SPn) and pyridine-2-thione (SPy) were synthesized and fully characterized to mimic the tungstoenzyme acetylene hydratase (AH). The complexes [W(CO)(C2 H2)(CHCH-SPy)(SPy)] (4) and [W(CO)(C2 H2)(CHCH-SPn)(SPn)] (5) were formed by intramolecular nucleophilic attack of the nitrogen donors of the ligand on the coordinated C2 H2 molecule. Labelling experiments using C2 D2 with the SPy system revealed the insertion reaction proceeding via a bis-acetylene intermediate. The starting complex [W(CO)(C2 H2)(SPy)2 ] (6) for these studies was accessed by the new acetylene precursor mixture [W(CO)(C2 H2)n (MeCN)3-n Br2 ] (n=1 and 2; 7). All complexes represent rare examples in the field of W-C2 H2 chemistry with 4 and 5 being the first of their kind. In the ongoing debate on the enzymatic mechanism, the findings support activation of acetylene by the tungsten center. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/31603595/Structural_Mimics_of_Acetylene_Hydratase:_Tungsten_Complexes_Capable_of_Intramolecular_Nucleophilic_Attack_on_Acetylene L2 - https://doi.org/10.1002/chem.201903264 DB - PRIME DP - Unbound Medicine ER -