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Enantiomerically Pure Bis(phosphanyl)carbaborane(12) Compounds


  • Parts of these results were previously reported at the XVI International Symposium on Homogeneous Catalysis in Florence/Italy, 6th–11th July 2008 as a poster presentation (P353) and XIII IMEBORON in Platja d'Aro/Spain, 21st–24th September 2008 as an oral poster presentation (P028).


Enantiomerically pure (RP,RP)- and (RP,SP)-1,2-bis[1-adamantyloxy-(–)-menthyloxyphosphanyl]-closo-dicarbaborane(12), 1,2-bis[bis(–)-menthyloxyphosphanyl]-closo-dicarbaborane(12)and 1,2-bis[bis(4-tert-butylphenyloxy)phosphanyl]-closo-dicarbaborane(12) were synthesised by the reaction of dilithiated 1,2-dicarba-closo-dodecaborane(12) with two equivalents of the corresponding chlorophosphite. The phosphonites are stable towards epimerisation, oxygen and water. P···P through-space coupling was observed, and the 3JPP coupling constants were determined by spectral simulation and DFT calculations. Late transition-metal complexes with molybdenum and rhodium were prepared to study the coordination properties of the bis(phosphanyl)carbaborane(12) compounds. Catalytic properties of various rhodium complexes were investigated in homogeneous catalytic hydroformylation reactions with various olefins. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)