Cyanuric acid (C H N O ) is widely used as cross-linker in basic polymers (often in combination with other crosslinking agents like melamine) but also finds application in more sophisticated materials such as in supramolecular assemblies and molecular sheets. The unknown phosphorus analogue of cyanuric acid, P C (OH) , may become an equally useful building block for phosphorus-based polymers or materials which have unique properties. Herein we describe a straightforward synthesis of 2,4,6-tri(hydroxy)-1,3,5-triphosphinine and its derivatives P C (OR) which have been applied as strong π-acceptor η -ligands in piano stool Mo(CO) complexes.
A simple synthesis of sodium 2-phosphanaphthalene-3-olate (1) based on the extrusion of N from phthalazine using Na[OCP] is reported. This heterocycle can be readily functionalized at the negatively charged oxygen center using a variety of electrophilic substrates. The coordination chemistry of both 1 and its neutral derivatives was explored, revealing their facile use as P-donor ligands for late-transition-metal complexes.
2-Chloroethylphosphine W(CO)5 complex readily reacts with sodium hydride. With one equivalent of NaH, the parent phosphirane complex is obtained. With more than two equivalents, the phosphiranide complex is exclusively formed. With 1.5 equivalents, a 1 : 1 mixture of and is obtained but readily attacks at the phosphorus atom by splitting of ethylene and by the formation of the P-P complex . In turn, the P-P bond of is split by NaH to yield the phosphide complex . The phosphiranide complex is a good source for a large variety of functional phosphirane complexes . With BrCN, the 1-cyanophosphirane complex is formed. Upon heating it loses its complexing group. Upon hydrolysis, it gives the 1-hydroxyphosphirane complex which dimerizes in basic medium by opening one P-C bond of the ring to give . The reaction of with PhPCl2 yields the triphosphorus complex whose molecular structure has been established by X-ray crystal structure analysis.
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