Enantiomerically Pure Bis(phosphanyl)carbaborane(12) Compounds

Abstract

Abstract Enantiomerically pure ( R P , R P )‐ and ( R P , S P )‐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 3 J PP 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)