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Reaction of cyclic (alkyl)(amino)phosphorous chloride 3 with GaCl 3 followed by the treatment with Me 3 NO afforded trimethylamine-stabilized oxophosphonium ion 5 , which was fully characterized by NMR spectroscopy and X-ray diffraction analysis. Computational study using DFT calculations indicates that the incorporation of a carbon atom next to the P center accumulates electron density on the P center. Oxophosphonium ion 5 is air and moisture stable but undergoes thermal decomposition to afford a phosphorus oxychloride 7 as well as a few single crystals of the by-product 8 . Reaction mechanisms for the formation of 7 and 8 may involve a Lewis base free oxophosphonium ion 6 . [ABSTRACT FROM AUTHOR]

A diastereoselective catalytic asymmetric hydrophosphination reaction was performed using a palladacycle catalyst to produce chiral PCP phosphine ligand with high dr (95:5) and excellent enantioselectivity (>99% ee). Subsequent facile metalation of the chiral ligand with Pt and Pd metal salts yielded the desired pincer complexes. The protonated form of these pincer complexes was also synthesised, and their structures were confirmed through the use of X-ray crystal diffraction and NMR spectroscopy analyses. [ABSTRACT FROM AUTHOR]