Co(III) Complexes with N2S3-Type Ligands as Structural/Functional Models for the Isocyanide Hydrolysis Reaction Catalyzed by Nitrile Hydratase
| Autor: | Yuko Wasada-Tsutsui, Tomohiro Ozawa, Yasuhiro Funahashi, Takuma Yano, Yuji Kajita, Tomohiro Ikeda, Tomonori Shibayama, Tomohiko Inomata, Hideki Masuda |
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| Rok vydání: | 2018 |
| Předmět: |
010405 organic chemistry
Chemistry Isocyanide Crystal structure 010402 general chemistry 01 natural sciences Medicinal chemistry Square pyramidal molecular geometry 0104 chemical sciences Catalysis Inorganic Chemistry Hydrolysis chemistry.chemical_compound Trigonal bipyramidal molecular geometry Octahedron Nitrile hydratase Physical and Theoretical Chemistry |
| Zdroj: | Inorganic Chemistry. 57:4277-4290 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.6b02324 |
| Popis: | It has been before reported that, in addition to hydration of nitriles, the Fe-type nitrile hydratase (NHase) also catalyzes the hydrolysis of tert-butylisocyanide (tBuNC). In order to investigate the unique isocyanide hydrolysis by NHase, we prepared three related Co(III) model complexes, PPh4[Co(L)] (1), PPh4[Co(L-O3)] (2), and PPh4[Co(L-O4)] (3), where L is bis(N-(2-mercapto-2-methylpropionyl)aminopropyl)sulfide. The suffixes L-O3 and L-O4 indicate ligands with a sulfenate and a sulfinate and with two sulfinates, respectively, instead of the two thiolates of L. The X-ray analyses of 1 and 3 reveal trigonal bipyramidal and square pyramidal structures, respectively. Complex 2, however, has five-coordinate trigonal-bipyramidal geometry with η2-type S–O coordination by a sulfenyl group. Addition of tBuNC to 1, 2, and 3 induces an absorption spectral change as a result of formation of an octahedral Co(III) complex. This interpretation is also supported by the crystal structures of PPh4[Co(L-O4)(tBuNC)] (4) ... |
| Databáze: | OpenAIRE |
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