Studies on bis(1′-ortho-carboranyl)benzenes and bis(1′-ortho-carboranyl)biphenyls

Abstract

. (2014) 'Studies on bis(1'-ortho-carboranyl)benzenes and bis(1'-ortho-carboranyl)biphenyls. ', Tetrahedron., 70 (34). pp. 5182-5189.Further information on publisher's website:http://dx.doi.org/10.1016/j.tet.2014.05.102Publisher's copyright statement: NOTICE: this is the author's version of a work that was accepted for publication in Tetrahedron. 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 Tetrahedron, 70, 34, 2014Tetrahedron, 70, 34, , 10.1016Tetrahedron, 70, 34, /j.tet.2014 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. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT AbstractReactions between the C,C'-dicopper(I) derivative of ortho-carborane and ortho-, meta-and para-diiodobenzene are reported. The reaction with 1,2-C 6 H 4

Exceptionally Long C−C Single Bonds in Diamino‐o‐carborane as Induced by Negative Hyperconjugation

“…Ishigaki, Suzuki, and co‐workers obtained a series of dispiro(acridan)‐substituted pyracene and acenaphthenes with C−C bond lengths of up to 180.6 pm . Also for closo ‐1,2‐dicarbadodecaboranes, with formally hexa‐coordinated carbon atoms and a multicenter bonding situation, many experimental results reveal C−C bonds that are longer than 174.8 pm . Previous density‐functional theory (DFT) computations indicated that 1,2‐(NH 2 ) 2 ‐ o ‐carboranes could have strikingly long C−C bonds .…”

Substituent Effects on the Fluorescence Properties of ortho‐Carbor­anes: Unusual Emission Behaviour in C‐(2′‐Pyridyl)‐ortho‐carboranes

“…Structured bands and higher coefficients (ε = 310-420 L mol -1 cm -1 ) were observed in 7 and 8 where π→π* transitions in the phenyl group present are responsible for these bands. [49,50] The absorption spectra for 9 or 10 showed one unstructured band slope tailing off at ca. 300 nm.…”

Recent advances in transition metal-mediated functionalization of o-carboranes

“…Electronic communication between the carborane cages via the para-phenylene bridge is found only in the para-substituted benzene compound. 14 CuCl-mediated C-C coupling of dilithiocarborane in toluene is a facile and practical method for the preparation of 1,1 0 -bis(o-carborane) (Scheme 5). The reaction intermediate 1,1 0 :2,2 0 -[Cu(toluene)] 2 (C 2 B 10 H 10 ) 2 is isolated from the reaction system before hydrolysis, which confirms the transmetalation process.…”