Institute of Chemistry - Inorganic Chemistry, NAWI Graz, University of Graz, Schubertstrasse 1, 8010 Graz (Austria).
Angew Chem Int Ed Engl. 2015 Oct 26;54(44):13018-21. doi: 10.1002/anie.201505764. Epub 2015 Sep 7.
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.
报道了一种仿生体系的合成与表征，该体系能够可逆地结合乙炔（acetylene）。该体系的设计模仿了钨酶乙炔水合酶的催化中间体。噻吩恶唑啉配体 S-Phoz（2-（4'，4'-二甲恶唑啉-2'-基）噻吩酚盐）用于在 W 中心周围生成仿生给体环境，有利于 W-乙炔加合物的稳定。从合成和结构的角度来看，特征配合物 [W(C2 H2 )(CO)(S-Phoz)2 ]（2）和[WO(C2 H2 )(S-Phoz)2 ]（3）非常罕见，因为人们对 W-C2 H2 加合物知之甚少。在可见光照射下，3 可以将 C2 H2 从其配位球中释放出来，生成 14 电子物种[WO(S-Phoz)2 ]（4）。在避光条件下，4 重新激活 C2 H2，这是第一个完全表征的乙炔可逆活化体系。
