We use cookies to ensure that we give you the best experience on our website. You can change your cookie settings at any time. Otherwise, we'll assume you're OK to continue.

Durham University

Department of Chemistry

Publication details for Dr Mark A. Fox

Harder, R.A., MacBride, J.A.H., Rivers, G.P., Yufit, D.S., Goeta, A.E., Howard, J.A.K., Wade, K. & Fox, M.A. (2014). Studies on bis(1’-ortho-carboranyl)benzenes and bis(1’-ortho-carboranyl)biphenyls. Tetrahedron 70(34): 5182-5189.

Author(s) from Durham


Reactions between the C,C’-dicopper(I) derivative of ortho-carborane and ortho-, meta- and para-diiodobenzene are reported. The reaction with 1,2-C6H4I2 unexpectedly afforded 2,2’-bis(1’-ortho-carboranyl)biphenyl, [HCB10H10CC6H4]22, whereas reactions with 1,3- or 1,4-C6H4I2 provided alternative routes to 1,3-bis(1’-ortho-carboranyl)benzene 3 and 1,4-bis(1’-ortho-carboranyl)benzene 4 respectively. The crystal structure of the biphenyl derivative 2 revealed significant distortions in the biphenylene framework attributable to the proximity of the two bulky carborane cages. UV absorption spectra and electrochemical data on 2 and 3 showed little electronic communication between the two carborane cages in either, and negligible pi-conjugation between the two ortho-phenylene rings in 2. However, substantial evidence was found of electronic communication between the carborane cages via the para-phenylene bridge in 4. B3LYP/6-31G* computations have been carried out on compounds 2 and 4, on 4,4’-bis(ortho-carboranyl)biphenyl 6 and on 1,2-bis(1’-ortho-carboranyl)benzene 7. Those on 2, 4 and 6 show the computed geometries to be in very good agreement with the experimental geometries: those on 7 allowed the reported molecular geometry of this compound to be revised and revealed a long cage C-C bond of 1.725(3)A.