The Synthesis and Structural Characterization of Polycyclic Derivatives of Cobalt Bis(dicarbollide)(1(-))

0443361 - ÚACH 2016 RIV US eng J - Článek v odborném periodiku
Grüner, Bohumír - Šícha, Václav - Hnyk, Drahomír - Londesborough, Michael Geoffrey Stephen - Císařová, I.
The Synthesis and Structural Characterization of Polycyclic Derivatives of Cobalt Bis(dicarbollide)(1(-)).
Inorganic Chemistry. Roč. 54, č. 7 (2015), s. 3148-3158. ISSN 0020-1669. E-ISSN 1520-510X
Grant CEP: GA AV ČR IAAX00320901; GA ČR GA15-05677S
Institucionální podpora: RVO:61388980
Klíčová slova: Organic-molecules * Crystal-structure * boron materials * Metallacarboranes
Kód oboru RIV: CA - Anorganická chemie
Impakt faktor: 4.820, rok: 2015

The cobalt bis(dicarbollide) anion [(1,2-C2B9H11)(2)-3,3'-Co](-)(1(-)) is an increasingly important building block for the design of new biologically active compounds. Here we report the reactions of lithiated 1 with N-(omega-bromoalkyl)phthalimides Br-(CH2)(n)-N(CO)(2)NC6H4 (where n = 1 to 3) that give a number of new compounds substituted at dicarbollide carbon atom positions. For n = 2 and 3, substitution of the cobalt bis(dicarbollide) anion is accompanied by cyclocondensation of the organic moieties to give polycyclic ring structures attached to the cage. Predominant products correspond to oxazolo[2,3-a]isoindol-5(9bH)-1,2,3-dihydro-9b-yl)-(1-cobalt(III) bis(1,2-dicarbollide)(1(-)) (2(-)) and 1-(2H-[1,3]-oxazino[2,3-a]isoindol-6(10bH)-1,3,4-dihydro-10b-yl)-(1-cobalt(III) bis(1,2-dicarbollide)(1(-)) (4(-)) ions with isoindolone functions containing either five- or six-membered lateral oxazine rings. Additionally, products (tetrahydro-2-benzo[4,5]furan-1(3H)-1-[3,3]-yl-)-1,1'-mu-cobalt(III) bis(1,2-dicarbollide)(1(-)) (3(-)) and (2-(azetidin-yl-carbonyl)benzoyl-)-1-cobalt(III) bis(1,2-dicarbollide)(1) (5) were isolated, which display unusual cyclic structures featuring a bicyclic benzofuranone ring attached in a bridging manner by a quarternary carbon to two skeletal carbon atoms and a ketobenzoic acid amide substituent with a side azetidine ring. However, in the case of n = 1, only the anticipated methylene amine derivative [(1-NH(2)CH2-1,2-C2B9H11)(1',2'-C2B9H11)(2)-3,3'-Co](-)(6(-)) was isolated in low yield after cleavage of the phthalimide intermediate species. The molecular structures of all isolated cyclic products 2 to 5 were confirmed by single-crystal X-ray diffraction studies, and the structure of cobalt bis(dicarbollide)-1-CH2NH2 6(-) was delineated using density functional theory applied at BP86/AE1 level in combination with NMR spectroscopy.
Trvalý link: http://hdl.handle.net/11104/0246468


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