New synthetic and structural studies on nitroso-ortho-carboranes RCB10H10CNO and bis(ortho-carboranyl)amines (RCB10H10C)2NH (R=Ph or Me)

Abstract

2009)'New synthetic and structural studies on nitroso-ortho-carboranes RCB10H10CNO and bis(ortho-carboranyl)amines (RCB10H10C)(2)NH (R = Ph or Me). ', Polyhedron., 28 (4). pp. 789-795. Further information on publisher's website:http://dx.doi.org/10. 1016/j.poly.2008.12.014 Publisher's copyright statement: NOTICE: this is the author's version of a work that was accepted for publication in Polyhedron. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reected in this document. Changes may have been made to this work since it was submitted for publication. A denitive version was subsequently published in Polyhedron, 28, 4, 2009Polyhedron, 28, 4, , 10.1016Polyhedron, 28, 4, /j.poly.2008 Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

Carbaboranes as Pharmacophores: Properties, Synthesis, and Application Strategies

“…The reduction of nitroso-carbaborane with tin powder and hydrochloric acid yields the primary amine. The use of diazonium salts as nitrogen source in the reaction with carbaboranyl nucleophiles gives azocarbaboranes, which can be reduced to the corresponding hydrazines. , …”

Trends in ortho-carboranes 1-X-2-R-1,2-C2B10H10 (R=Ph, Me) bearing an exo-CN-bonded substituent group (X=NO, NNR′ or NHR′′)

“…We then explore the structural, bonding and [4,10]. We also compare the structural and bonding relationships of these 3D pseudoaromatic cages with 2D aromatic ring analogues.…”

“…1-Methylortho-carborane [25] and 1-phenyl-ortho-carborane [26] were prepared by literature methods and dried by sublimation at 0.01 mm Hg. 1-Nitroso-2-methyl-orthocarborane and 1-nitroso-2-phenyl-ortho-carborane were made as described elsewhere [10]. Benzenediazonium tetrafluoroborate and 4-methylbenzenediazonium tetrafluoroborate salts were made using a general literature method [27].…”

“…Synthetic methods that have not been reported in our earlier papers [4,10] are described in detail in the Experimental section. The azocarboranes were synthesised using a reported literature procedure [12].…”

Distortions, deviations and alternative facts: reliability in crystallography

“…The use of a phenyl substituent has the added bonus of improving crystallization by offering the prospect of intermolecular aromatic ringstacking interactions. The results for a series of compounds with strongly electron-donating substituents (X) are unambiguous and very marked, with a considerable elongation of the C-C bond, to as much as 2.001 Å (from around 1.7 Å ) for a deprotonated OH substituent that behaves essentially as a pentuply bridging carbonyl group in the cage (Brown et al, 1987;Coult et al, 1992;Boyd et al, 2004;Fox, MacBride et al, 2009;; the 'proton sponge' salt of this anion is shown in Fig. 6.…”