Year: 2024
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide The dianion [Fe 2 [(μ-SeCH 2 ) 2 NH](CN) 2 (CO) 4 ] 2– ([ 2 ] 2– ) is of interest for the preparation of the selenide analog of the active site of the [FeFe]-hydrogenases. The obvious route for its synthesis by cyanation of Fe 2 [(μ-SeCH 2 ) 2 NH](CO) 6 ( 3 ) fails for reasons that this paper explains and resolves. We show that CN – cleaves Se–C bonds in 3 . For example, treatment of Fe 2 [(μ-SeCH 2 ) 2 NH](CO) 6 with NEt 4 CN followed by CH 3 I gives substantial amounts of Fe 2 (μ-SeCH 3 ) 2 (CO) 6 . Authentic [ 2 ] 2– can be obtained by cyanation of Fe 2 [(μ-SeCH 2 ) 2 NH](CO) 5 (pyridine). The 77 Se NMR data for [ 2 ] 2– and 3 are reevaluated and explained. Attempts to prepare Fe 2 [(μ-SeCH 2 ) 2 NH](PPh 3 ) 2 (CO) 4 ( 9 ) by Me 3 NO-induced decarbonylation of 3 also suffers from degradation of the organoselenium ligand. Complex 9 was prepared instead by photosubstitution. The protonation of [ 2 ] 2– and [Fe 2 [(μ-SCH 2 ) 2 NH](CN) 2 (CO) 4 ] 2– are compared: the selenium compounds are more basic. The structure of [HFe 2 [(μ-SCH 2 ) 2 NH](CN) 2 (CO) 4 ] − was determined crystallographically.
Source: Organometallics
Authors: Xin Yu, Toby J. Woods, Thomas B. Rauchfuss
Institution: University of Illinois Urbana-Champaign
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W4405713802