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exo-closo-rhodacarboranes: synthesis and characterisation of [{exo-(R3P)(2)Rh}(closo-CB11H12)][R3P = P(OMe)(3), PCy3, 1/2dppe]


Reference:

Rifat, A., Laing, V. E., Kociok-Kohn, G., Mahon, M. F., Ruggiero, G. D. and Weller, A. S., 2003. exo-closo-rhodacarboranes: synthesis and characterisation of [{exo-(R3P)(2)Rh}(closo-CB11H12)][R3P = P(OMe)(3), PCy3, 1/2dppe]. Journal of Organometallic Chemistry, 680 (1-2), pp. 127-135.

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Abstract

Addition of H-2 to CH2Cl2 solutions of [(diene)Rh(L)(2)][closo-CB11H12] (diene=norbornadiene, cyclooctadiene, L=PCy3, P(OMe)(3), 1/2dppe) results in the formation of the exo-closo complexes [(PR3)(2)Rh(closo-CB11H12)]. These have been characterised in solution by H-1- and B-11-NMR spectroscopy, and for L = PCy3 by a single crystal X-ray diffraction study. This suggests that the metal fragment is bound with the cage through the 7,8- and not the 7,12-{BH} vertices. DFT calculations on a model system where L=PMe3 show that there is only a negligible energy difference between these two isomers (I kcal mol(-1)), suggesting that both represent stable structures. The salient spectroscopic markers that indicate an interaction of [closo-CB11H12](-) with a metal fragment are discussed and compared across a range of metal complexes. Large upfield shifts in the B-11-NMR spectrum and a small downfield shift of the CH vertex in the H-1-NMR spectrum are shown to the most reliable indicators of borane interaction in solution. (C) 2003 Elsevier Science B.V. All rights reserved.

Details

Item Type Articles
CreatorsRifat, A., Laing, V. E., Kociok-Kohn, G., Mahon, M. F., Ruggiero, G. D. and Weller, A. S.
DOI10.1016/s0022-328x(03)00230-4
DepartmentsFaculty of Science > Chemistry
RefereedYes
StatusPublished
ID Code4967
Additional InformationID number: ISI:000185272400017

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