Synthesis and reactivity of propionitrilium derivatives of cobalt and iron bis(dicarbollides)

• Published in: New journal of chemistry 2020-10, Vol.44 (37), p.15836-15848
• Main Authors: Bogdanova, Ekaterina V, Stogniy, Marina Yu, Chekulaeva, Lyubov A, Anisimov, Aleksei A, Suponitsky, Kyrill Yu, Sivaev, Igor B, Grin, Mikhail A, Mironov, Andrey F, Bregadze, Vladimir I
• Format: Article
• Language: English
• Subjects: Alcohols; Cesium; Cobalt; Column chromatography; Columnar structure; Crystallography; Crystals; Derivatives; Iron; Isomers; Molecular structure; Retirement; Silicon dioxide; Single crystals; Synthesis; Thiols
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/d0nj03017a

The synthesis of propionitrilium derivatives of cobalt and iron bis(dicarbollides) [8-EtC&z.tbd; N -3,3′-M(1,2-C 2 B 9 H 10 )(1′,2′-C 2 B 9 H 11 )] (M = Co, Fe) by the reaction of the cesium salts of the parent bis(dicarbollide) anions [3,3′-M(1,2-C 2 B 9 H 11 ) 2 ] − with propionitrile in the presence of tert -butyl bromide is described. The nucleophilic addition reactions of water, alcohols, and thiols with the -N + &z.tbd;C triple bond of the prepared nitrilium derivatives were studied and the corresponding iminols [8-EtC(OH)&z.dbd;HN-3,3′-M(1,2-C 2 B 9 H 10 )(1′,2′-C 2 B 9 H 11 )] (M = Co, Fe), imidates [8-EtC(OR)&z.dbd;HN-3,3′-M(1,2-C 2 B 9 H 10 )(1′,2′-C 2 B 9 H 11 )] (M = Co, R = Me, Et, i-Pr, Bu; M = Fe, R = Et), and thioimidates [8-EtC(SR)&z.dbd;HN-3,3′-Co(1,2-C 2 B 9 H 10 )(1′,2′-C 2 B 9 H 11 )] (R = Et, Bu, Hx) were synthesized as mixtures of E and Z -isomers, some of which could be separated by the column chromatography on silica. The molecular structure of [( Z )-8-EtC(OiPr)&z.dbd;HN-3,3′-Co(1,2-C 2 B 9 H 10 )(1′,2′-C 2 B 9 H 11 )] was determined by single-crystal X-ray diffraction study. The nucleophilic addition of alcohols and thiols to 8-propionitrilium derivatives of cobalt and iron bis(dicarbollides) gives the corresponding imidates and thioimidates.