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Hip to be square: Direct carbonylation of solutions of the heptaphosphide trianion (P7(3-)) afforded the phosphaethynolate anion in moderate yields. This species undergoes [2+2] cycloaddition reactions with diphenylketene and bis(2,6-diisopropylphenyl)carbodiimide to yield the anionic four-membered heterocycles P[C(O)]2C(C6H5)2(-) and PC(O)(CNDipp)NDipp(-) .
We show that the 2-phosphaethynolate anion, OCP-, is a simple and efficient catalyst for the cyclotrimerization of isocyanates. This process proceeds step-wise and involves five-membered heterocycles, namely 1,4,2-diazaphospholidine-3,5-dionide anions and spiro-phosphoranides as detectable intermediates, both of which were also found to be involved in the… (More)
We describe the coordination chemistry of the primary phosphine PH2C(O)NH2 (phosphinecarboxamide) towards group 6 transition-metals. Experimental and theoretical studies reveal that this novel species has comparable electronic properties to PH3.
Lanthanide complexes of tetrapicolyl cyclen displayed remarkably high affinities for fluoride (log K≈5) in water, and were shown to form 1:1 complexes. The behaviour of these systems can be rationalised by changes to the magnitude of the crystal-field parameter, B20 . However, such changes are not invariably accompanied by a change in sign of this… (More)
Reactions of the 2-phosphaethynolate anion (PCO(-), 1) with ammonium salts quantitatively yielded phosphinecarboxamide (PH2C(O)NH2, 2). The molecular structure and chemical properties of 2 were studied by single-crystal X-ray diffraction and multielement NMR spectroscopy. This phosphorus-containing analogue of urea is a rare example of an air-stable primary… (More)
We demonstrate that the synthesis of new N-functionalized phosphinecarboxamides is possible by reaction of primary and secondary amines with PCO(-) in the presence of a proton source. These reactions proceed with varying degrees of success, and although primary amines generally afford the corresponding phosphinecarboxamides in good yields, secondary amines… (More)
We describe the reactivity of the 2-phosphaethynolate anion (PCO-) towards enantiomerically pure α-amino acids (AAs) resulting in the formation of novel salts of phosphinecarboxamides bearing chiral functionalities. These transformations occurred quantitatively with all but one of the amino acids trialled (the basic amino acid arginine was found to be… (More)