Pendant Functionalised Triphosphamacrocycles

Abstract

The selective functionalisation of a single phosphorus atom in the parent [Mo(CO)3(12aneP3H3)], where 12aneP3H3 is 1,5,9-triphosphacyclododecane, has been achieved by deprotonation and subsequent reaction with an ether containing an alkyl halide group. Yields of the monosubstituted products are very sensitive to the reaction conditions, which must be carefully controlled in order to achieve reasonable selectivity. In addition, trisubstitution of [M(CO)3(12aneP3H3)] with carbon chains containing pendant donors such as ethers, thioethers, amines and phosphanes has been achieved by both deprotonation/addition (M = Mo0) and hydrophosphination (M = Cr0) protocols. The new compounds have been characterised by spectroscopic and analytical techniques, including X-ray crystallography, and a selection of the P3 macrocycles released from their templates by oxidation and base digestion.