Synthesis, Characterisation and Reactivity towards PdII and PtII of ortho-, meta- and para-Xylyl-Based Phosphorus-Containing Macrocycles

Abstract

The new meta-and para-xylyl-based phosphadithiamacrocycles 6-phenyl-6-phospha-3,9-dithiabicyclo[9,3,1]pentadeca-1(15),12,14-triene (L2) and 6-phenyl-6-phospha-3,9-dithiabicyclo[9,2,2]pentadeca-1(13),12,14-triene (L3) have been synthesised and characterised. The reactivity of these ligands and the previously described ortho-xylyl macrocycle 6-phenyl-6-phospha-3,9-dithiabicyclo[9,4,0]pentadeca-1(11), 12,14-triene (L1) with [PdCl 2 (cod)] and K 2 [PtCl 4 ] has been studied. [MCl 2 (L)] complexes have been obtained and characterised by NMR spectroscopy. X-ray structural analyses have been carried out in the case of [PdCl 2 L2]·CH 3 CN

Phosphines and Related Tervalent Phosphorus Systems

“…374 Phosphadithiamacrocycles have also been assembled by the reactions of the isomeric bis(chloromethyl)benzenes with the thiolate anions derived from bis(2-mercaptoethyl)phenylphosphine. 375 Very many new phosphines have been prepared utilising the reactivity of functional groups in the ortho-or para-positions to phosphorus in an arylphosphine. Thus, e.g., the spiro-phosphino-oxazine (160) has been obtained by the reaction of ortho-diphenylphosphinobenzonitrile with a spiro-aminoalcohol, 376 new chiral arylphosphino-phosphito ligands have been prepared from the reactions of chiral ortho-phosphinophenols with chlorophosphites, 377 and treatment of o-(diphenylphosphino)benzyl chloride with various 1-substituted imidazoles has given a series of phosphino-imidazolium salts (161), potential precursors of nucleophilic carbene ligands.…”