16872-10-9Relevant articles and documents
PREPARATION AND CRYSTAL STRUCTURE OF THE DICARBORANYLMAGNESIUM BIS(DIOXANE) ADDUCT Mg(2-Me-1,2-C2B10H10)2*2C4H8O2
Clegg, William,Brown, David A.,Bryan, Stephen J.,Wade, Kenneth
, p. 39 - 46 (1987)
The preparation of Mg(2-Me-1,2-C2B10H10)2*2C4H8O2 from the carboranyl Grignard reagent RMgBr (R = the methyl-ortho-carboranyl residue, 2-Me-1,2-C2B10H10) by a dioxane-induced disproportionation reaction is described.An X-ray crystallographic study of the product has revealed a monomeric molecular structure R2MgL2 (L=1,4-dioxane, C4H8O2) in which the carboranyl groups and dioxane ligands provide the central magnesium atom with a distorted tetrahedral coordination sphere of two carbon and two oxygen atoms, with bond lengths Mg-C 2.156(5) Angstroem, Mg-O 2.038(8) Angstroem and bond angles CMgC 123.5(4) deg, OMgO 99.5(5) deg, distortions from regular tetrahedral angles attributable to the relative bulk of the carboranyl ligands.
Rhodium-Catalyzed Regioselective Hydroxylation of Cage B?H Bonds of o-Carboranes with O2or Air
Lyu, Hairong,Quan, Yangjian,Xie, Zuowei
, p. 11840 - 11844 (2016)
A rhodium-catalyzed hydroxylation of a cage B4?H bond in o-carboranes with either O2or air as the oxygen source is described, and serves as a new methodology for the regioselective generation of a series of 4-OH-o-carboranes in a one-pot process. The use of either O2or air as both the oxidant and the oxygen source makes this protocol very environmentally friendly and practical.
Light-enabled alkenylation of iodocarboranes with unactivated alkenes
Lu, Zhenpin,Ni, Hangcheng,Xie, Zuowei
, p. 104 - 110 (2021/12/27)
The synthesis of alkenylated-o-carboranesviaphotoalkenylation of iodocarboranes with unactivated alkenes has been achieved. This strategy features a transition metal-free protocol, a light-promoted reaction under mild reaction conditions, broad substrate scope and good functional group tolerance. Control experiments suggest that the reaction may involve the cage C-centered radical species.
Formal insertion of o-carborynes into ferrocenyl C-H bonds: A simple access to o-carboranylferrocenes
Wang, Sunewang Rixin,Xie, Zuowei
, p. 4544 - 4550 (2012/07/14)
Insertion of o-carborynes (1,2-dehydro-o-carboranes) into ferrocenyl C-H bonds has been described, providing a convenient methodology for the preparation of functionalized ferrocenyl o-carboranes. Reaction of the carboryne precursors 1-I-2-Li-9,12-Me2-1,2-C2B10H8 or 1-I-2-Li-3-R-1,2-C2B10H9 (R = H, Ph, Me, Cl, Br, and I) with 2.5 equiv of ferrocene at 80 °C in cyclohexane afforded [1-(η5-C5H4)(9,12-Me2-1,2-C 2B10H9)]Fe(η5-C 5H5) and [1-(η5-C5H 4)(3-R-1,2-C2B10H10)] Fe(η5-C5H5) (R = H, Ph, Me, Cl, Br, and I) in 19-44% isolated yields. On the other hand, in addition to the desired C-H bond insertion products [1-(η5-C5H4)(3-X-1, 2-C2B10H10)]Fe(η5-C 5H5), bis(ferrocenyl)-o-carboranes 1,2- [(η5-C5H5)Fe(η5-C 5H4)]2-3-X-1,2-C2B 10H9 were isolated from the reactions of 1-I-2-Li-3-X-1,2-C2B10H9 (X = Cl, Br, and I) in 12%, 15%, and 8% yields, respectively. Treatment of 1,2-dilithio-o-carborane or 1-lithio-2-methyl-o-carborane with ferrocenium hexafluorophosphate in cyclohexane also generated [1-(η5-C5H 4)(1,2-C2B10H11)] Fe(η5-C5H5) and [1-(η5- C5H4)(2-Me-1,2-C2B10H 10)]Fe(η5-C5H5) in 17% and 31% isolated yields, respectively. On the basis of these observations, it is suggested that the single-electron oxidation of ferrocene to the electrophilic ferrocenium cation by o-carborynes is crucial for the insertion reaction. Accordingly, a reaction mechanism is proposed.
