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Towards Structural‐Functional Mimics of Acetylene Hydratase: Reversible Activation of Acetylene using a Biomimetic Tungsten Complex
Author(s) -
Peschel Lydia M.,
Belaj Ferdinand,
MöschZanetti Nadia C.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201505764
Subject(s) - acetylene , chemistry , adduct , catalysis , ligand (biochemistry) , photochemistry , coordination sphere , combinatorial chemistry , molecule , organic chemistry , biochemistry , receptor
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(C 2 H 2 )(CO)(S‐Phoz) 2 ] ( 2 ) and [WO(C 2 H 2 )(S‐Phoz) 2 ] ( 3 ) are extremely rare from a synthetic and structural point of view as very little is known about W–C 2 H 2 adducts. Upon exposure to visible light, 3 can release C 2 H 2 from its coordination sphere to yield the 14‐electron species [WO(S‐Phoz) 2 ] ( 4 ). Under light‐exclusion 4 re‐activates C 2 H 2 making this the first fully characterized system for the reversible activation of acetylene.