Andrew R. Jupp

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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(-) .
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)
The indium compounds In(N(SiMe3 )2 )2 Cl⋅THF (2) and In(N(SiMe3 )2 )Cl2 ⋅(THF)n (3) were shown to react with CO2 to give [(Me3 Si)2 N)InX(μ-OSiMe3 )]2 (X=N(SiMe3 )2 4, Cl 5). 0.05-2.0 mol % of the species 3 acts as a pre-catalyst for the conversion of aryl and alkyl silylamines under CO2 (2-3 atm) to give the corresponding ureas in 70-99 % yields. A(More)
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)
A synthesis of the 2-phosphathioethynolate anion, PCS–, under ambient conditions is reported. The coordination chemistry of PCO–, PCS– and their nitrogen-containing congeners is also explored. Photolysis of a solution of W(CO)6 in the presence of PCO– [or a simple ligand displacement reaction using W(CO)5(MeCN)] affords [W(CO)5(PCO)] (1). The cyanate and(More)
Experimental details................................................................................................................................2 Materials and methods............................................................................................................................2 Experimental(More)
The reactions of the phosphaethynolate anion ([PCO]- ) with a range of boranes were explored. BPh3 and [PCO]- form a dimeric anion featuring P-B bonds and is prone to dissociation at room temperature. The more Lewis acidic borane B(C6 F5 )3 yields a less symmetric dimer of [PCO]- with P-B and P-O bonds. Less sterically demanding HB(C6 F5 )2 and H2 B(C6 F5 )(More)
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 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)