Search results for "boranes"
showing 10 items of 45 documents
Stereoselective synthesis of o-bromo (or iodo)aryl P-chirogenic phosphines based on aryne chemistry.
2012
The efficient synthesis of chiral or achiral tertiary phosphines bearing an o-bromo (or iodo)aryl substituent is described. The key step of this synthesis is based on the reaction of a secondary phosphine borane with the 1,2-dibromo (or diiodo)arene, owing to the formation in situ of an aryne species in the presence of n-butyllithium. When P-chirogenic secondary phosphine boranes were used, the corresponding o-halogeno-arylphosphine boranes were obtained without racemization in moderate to good yields and with ee up to 99%. The stereochemistry of the reaction, with complete retention of the configuration at the P atom, has been established by X-ray structures of P-chirogenic o-halogenopheny…
Characterization of β-B-Agostic Isomers in Zirconocene Amidoborane Complexes
2009
The reaction of Cpx2ZrCl2 (Cpx = Cp, Cp*) with ammonia borane in presence of n-butyllithium yielded Cp2Zr(Cl)NH2BH3 and Cpx2Zr(H)NH2BH3. These derivatives are isoelectronic with the ethyl zirconocene chloride and hydride, respectively, and feature a chelating amidoborane ligand coordinating through a Zr−N bond and a Zr−H−B bridge. In solution, each of the complexes consists of an equilibrium mixture of two isomers differing in the orientation of the amidoborane ligand with respect to the Zr−X bond (X = H, Cl), while in the solid state, only one isomer was observed. Such isomers have not been characterized for any metal complexes containing the isoelectronic β-agostic ethyl ligand or any oth…
Carboranylphosphinic Acids: A New Class of Purely Inorganic Ligands
2015
Purely inorganic carboranyl phosphinates were prepared, and the influence of the cluster on the reactivity of the phosphinate group was studied. Electron-withdrawal by the carboranyl carbon atoms, combined with space-filling efficiency and enhanced aromaticity of the cluster cage, renders the phosphorus more difficult to oxidize. This enables carboranyl phosphinates to survive harsh oxidizing conditions, a property which is uncommon in organic phosphinates.
Poly-iodinated closo 1,2-C 2 B 10 and nido [7,8-C 2 B 9 ] − carborane frameworks: Synthesis and consequences
2015
Abstract The preparation of Cc-monosubstituted closo and nido carborane derivatives, mono-, di and tetraiodinated is reported. Some of these mono-to poly-iodinated nido carboranes are studied in terms of the acidity of the open face bridging proton, their chemical shift position in the 1H NMR, and the lesser tendency to η5-coordination in parallel to a larger number of iodo groups.
Synthesis of Globular Precursors
2015
o-Carborane (C2 B10 H12 ) was adapted to perform as the core of globular macromolecules, dendrons or dendrimers. To meet this objective, precisely defined substitution patterns of terminal olefin groups on the carborane framework were subjected to Heck cross-coupling reactions or hydroboration leading to hydroxyl terminated arms. These led to new terminal groups (chloro, bromo, and tosyl leaving groups, organic acid, and azide) that permitted ester production, click chemistry, and oxonium ring opening to be performed as examples of reactions that demonstrate the wide possibilities of the globular icosahedral carboranes to produce new dendritic or dendrimer-like structures. Polyanionic speci…
Enantiodivergent synthesis of P-chirogenic phosphines
2010
International audience; Several approaches for the enantiodivergent synthesis of P-chirogenic mono- and diphosphines are described, using ephedrine methodology and phosphine borane chemistry. Firstly, both enantiomers of a tertiary phosphine can be obtained starting from the same oxazaphospholidine borane complex, prepared from (+)-ephedrine, when changing the order of addition of the organolithium reagents during the synthetic pathway. The second approach is based on the chlorophosphine boranes, which react with an organolithium reagent, to afford the corresponding phosphines with inversion of configuration. In the case where the chlorophosphine borane reacts with the t-butyl lithium reage…
Quantum Chemistry of Excited States in Polyhedral Boranes
2015
In this Chapter we describe the electronic structure of ground states and excited states of the two isomers of octadecaborane (22), anti- and syn-B18H22, and the new derivative of anti-B18H22, the polyhedral substituted borane 4,4′-(HS)2-anti-B18H20. A theoretical interpretation is given on the fluorescence of the anti-B18H22 isomer, and the non-radiative decay of the syn-B18H22 isomer, an unsolved problem since 1962. For the new derivative of anti-B18H22, substitution of hydrogen atoms in positions 4 and 4′ by SH groups allows the tuning of the photophysical properties in 4,4′-(HS)2-anti-B18H20, facilitating intersystem crossing from the excited singlet state to the triplet state.
The complexation of tetraphenylborate with organic N-heteroaromatic cations
2001
Complexation studies of eleven N-heteroaromatic cations with tetraphenylborate are reported. Tetraphenylborate forms complexes with five cations and reacts to form Lewis-base boranes with six cations. The complexes and the displacement reaction products were characterised by 1H NMR spectroscopy, elemental analysis and crystallographic methods. In the complexes C–H⋯π or N–H⋯π hydrogen bonds are the principal intermolecular interactions. The stability constants for the complexes are determined by 1H NMR titration in acetonitrile–methanol (1 ∶ 1) solution. Crystal structures of four of the complexes and three of the Lewis-base triphenylborane products are reported.
From Mono- to Poly-Substituted Frameworks: A Way of Tuning the Acidic Character of C-c-H in o-Carborane Derivatives
2009
[EN] The incorporation of iodine atoms onto the boron vertices of the o-carborane framework causes, according to spectroscopic data, a uniform increase in the acidic character of the C-c-H (C-c= cluster carbon) vertices, whereas the incorporation of methyl groups onto the boron vertices of the o-carborane framework reduces their acidity. Methyl groups when attached to boron are electron-withdrawing in boron clusters, whereas iodine atoms bonded to boron act as electron donors. This has been proven on B-methyl and B-iodinated o-carboranes with NMR spectroscopy measurements and DFT calculations of natural bond orbital (NBO) charges. which show a Cumulative buildup of positive cluster only tot…
closo-borane conjugated regulatory peptides retain high biological affinity: synthesis of closo-borane conjugated Tyr(3)-octreotate derivatives for B…
2008
Despite the improvements in cancer therapy during the past years, high-grade gliomas and many other types of cancer are still extremely resistant to current forms of therapy. Boron neutron capture therapy (BNCT) provides a promising way to destroy cancer cells without damaging healthy tissue. However, BNCT in practice is still limited due to the lack of boron-containing compounds that selectively deliver boron to cancer cells. Since many neuroendocrine tumors show an overexpression of the somatostatin receptor, it was our aim to synthesize compounds that contain a large number of boron atoms and still show high affinity toward this transmembrane receptor. The synthetic peptide Tyr (3)-octre…