title: Towards Structural-Functional Mimics of Acetylene Hydratase: Reversible Activation of Acetylene using a Biomimetic Tungsten Complex.
abstract: The synthesis and characterization of a biomimetic system that can reversibly bind acetylene (ethyne) is reported. The system has been designed to mimic catalytic intermediates of the tungstoenzyme acetylene hydratase. The thiophenyloxazoline ligand S-Phoz (2-(4',4'-dimethyloxazolin-2'-yl)thiophenolate) is used to generate a bioinspired donor environment around the W center, facilitating the stabilization of W-acetylene adducts. The featured complexes [W(C2 H2 )(CO)(S-Phoz)2 ] (2) and [WO(C2 H2 )(S-Phoz)2 ] (3) are extremely rare from a synthetic and structural point of view as very little is known about W-C2 H2 adducts. Upon exposure to visible light, 3 can release C2 H2 from its coordination sphere to yield the 14-electron species [WO(S-Phoz)2 ] (4). Under light-exclusion 4 re-activates C2 H2 making this the first fully characterized system for the reversible activation of acetylene.
authors.affiliation: Institute of Chemistry - Inorganic Chemistry, NAWI Graz, University of Graz, Schubertstrasse 1, 8010 Graz (Austria).
authors.forename: Lydia M
authors.initials: LM
authors.lastname: Peschel
authors.affiliation: Institute of Chemistry - Inorganic Chemistry, NAWI Graz, University of Graz, Schubertstrasse 1, 8010 Graz (Austria).
authors.forename: Ferdinand
authors.initials: F
authors.lastname: Belaj
authors.affiliation: Institute of Chemistry - Inorganic Chemistry, NAWI Graz, University of Graz, Schubertstrasse 1, 8010 Graz (Austria). nadia.moesch@uni-graz.at.
authors.forename: Nadia C
authors.initials: NC
authors.lastname: Mösch-Zanetti
mesh_terms: D000114:Acetylene / Q000737:chemistry* / Q000378:metabolism; D040761:Biomimetic Materials / Q000737:chemistry* / Q000378:metabolism; D056831:Coordination Complexes / Q000737:chemistry* / Q000378:metabolism; D006836:Hydro-Lyases / Q000737:chemistry* / Q000378:metabolism; D008968:Molecular Conformation; D014414:Tungsten / Q000737:chemistry* / Q000378:metabolism
chemical_list: D056831:Coordination Complexes; D006836:Hydro-Lyases; C096200:acetylene hydratase; D000114:Acetylene; D014414:Tungsten
keywords: S ligands; acetylene hydratase; bioinorganic chemistry; small-molecule activation; tungsten