16390-61-7Relevant articles and documents
1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C2B10H11. Synthesis, Characterization, and Structure As Determined in the Gas Phase by Electron Diffraction, in the Crystalline Phase at 199 K by X-ray Diffraction, and by ab Initio Computations
Brain, Paul T.,Cowie, Jill,Donohoe, David J.,Hnyk, Drahomír,Rankin, David W.H.,Reed, David,Reid, Bruce D.,Robertson, Heather E.,Welch, Alan J.,Hofmann, Matthias,Von Schleyer, Paul Ragué
, p. 1701 - 1708 (1996)
The compound 1-phenyl-1,2-dicarba-closo-dodecaborane(12), 1-C6H5-1,2-closo-C2B10H11 (1), has been synthesized and characterized by a complete assignment of its 11B NMR spectrum via 11B{1H}/11B{1H} (COSY), 1H{11Bselective} and 1H{11B}/1H{11B} (COSY) spectroscopy. An electron- and X-ray diffraction investigation of 1, complemented by ab initio calculations, has been undertaken. The gas-phase electron-diffraction (GED) data can be fitted by several models describing conformations which differ in the position of the phenyl ring with respect to the carborane cage. Local symmetries of C2v and D6h for the 1,2-C2B10 and C6 moieties, respectively, were adopted in the GED model in order to simplify the problem. In addition, constraints among the close-lying C-C and B-B bonds were employed. However, even though such simplifications led to satisfactory refinements (RG = 0.069- 0.071), a unique, definitive solution could not be gained. The (C-C)mean, (C-B)mean and (B-B)mean bond lengths, ra, are ca. 1.44, 1.72, and 1.78 ?, respectively. The C6 hexagon, with ra(C-C) = ca. 1.394 ?, either eclipses the C(1)-C(2) vector (overall Cs symmetry) or more or less eclipses the C(1)-B(4) cluster bond (overall C1 symmetry). In contrast, in the solid at 199 K, the ring lies at a position intermediate between the two GED positions, as determined by X-ray crystallography [C8H16B10, monoclinic P21/a: a = 12.047(3) ?, b = 18.627(4) ?, c = 12.332(5) ?, β = 110.09(4)°, Z = 8]. The C-B distances span the range 1.681(6)-1.743(5) ?, and B-B lengths lie between 1.756(6) and 1.795(6) ?. A similar conformation was found for the theoretical (RHF/6-31G* level) structure which was fully optimized in C1 symmetry. The re distances are consistent with the dimensions derived in the experimental studies. IGLO calculations of the 11B chemical shifts, in addition to SCF single-point energies of the GED structures, further support these observations.
Light-promoted copper-catalyzed cage C-Arylation of: O-carboranes: facile synthesis of 1-Aryl-o-carboranes and o-carborane-fused cyclics
Lu, Zhenpin,Ni, Hangcheng,Xie, Zuowei
supporting information, p. 14944 - 14948 (2021/09/04)
Light-promoted, copper catalyzed cage C-H arylation of o-carboranes with aryl halides has been achieved, leading to the facile synthesis of a variety of 1-Aryl-o-carboranes and o-carborane-fused cyclics. This method has the following features: (1) using o
Photoarylation of Iodocarboranes with Unactivated (Hetero)Arenes: Facile Synthesis of 1,2-[(Hetero)Aryl]n-o-Carboranes (n=1,2) and o-Carborane-Fused Cyclics
Ni, Hangcheng,Qiu, Zaozao,Xie, Zuowei
supporting information, p. 712 - 716 (2017/01/14)
Photoarylation of iodocarboranes with unactivated arenes/heteroarenes at room temperature has been achieved, for the first time, thus leading to the facile synthesis of a large variety of cage carbon mono(hetero)arylated and di(hetero)arylated o-carboranes. This work represents a clean, efficient, transition-metal-free, and cheap synthesis of functionalized carboranes, which has significant advantages over the known methods.
Syntheses and reductions of C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes
Kahlert, Jan,B?hling, Lena,Brockhinke, Andreas,Stammler, Hans-Georg,Neumann, Beate,Rendina, Louis M.,Low, Paul J.,Weber, Lothar,Fox, Mark A.
, p. 9766 - 9781 (2015/06/08)
Two C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes, 1-(BMes2)-2-R-1,2-C2B10H10 (1, R = H, 2, R = Ph), were synthesised by lithiation of 1,2-dicarba-closo-dodecaborane and 1-phenyl-1,2-dicarba-closo-dodecaborane, respectively, with n-butyllithium and subsequent reaction with fluorodimesitylborane. These novel compounds were structurally characterised by X-ray crystallography. Compounds 1 and 2 are hydrolysed on prolonged exposure to air to give mesitylene and boronic acids 1-(B(OH)2)-2-R-1,2-C2B10H10 (3, R = H, 4, R = Ph respectively). Addition of fluoride anions to 1 and 2 resulted in boryl-carborane bond cleavage to give dimesitylborinic acid HOBMes2. UV absorption bands at 318-333 nm were observed for 1 and 2 corresponding to local π-π-transitions within the dimesitylboryl groups while visible emissions at 541-664 nm with Stokes shifts of 11 920-16 170 cm-1 were attributed to intramolecular charge transfer transitions between the mesityl and cluster groups. Compound 2 was shown by cyclic voltammetry to form a stable dianion on reduction. NMR spectra for the dianion [2]2- were recorded from solutions generated by reductions of 2 with alkali metals and compared with NMR spectra from reductions of 1,2-diphenyl-ortho-carborane 5. On the basis of observed and computed 11B NMR shifts, these nido-dianions contain bowl-shaped cluster geometries. The carborane is viewed as the electron-acceptor and the mesityl group is the electron-donor in C-dimesitylboryl-1,2-dicarba-closo-dodecaboranes.
