N,N',N'-TRIMETHYLETHYLENEDIAMINE-SUBSTITUTED PHOSPHORUS(III) COMPOUNDS AND THEIR OXIDATION TO DERIVATIVES WITH 4-COORDINATED AND 5-COORDINATED PHOSPHORUS

A study was made of the intramolecular donor-acceptor interaction in N,N',N'-trimethylethylenediamine-substituted phosphorus compounds, involving lambda-3-, lambda-4- and lambda-5-phosphorus atoms, as a function of the nature of the substituents at phosphorus. The reaction of N-trimethylsilyl-N,N',N'-trimethylethylenediamine (1) with (Pr(i)O)2PCl furnished the acyclic, trimethylethylenediamine-substituted phosphorus(III) compound 4. There is no NMR spectroscopic evidence for an intramolecular donor-acceptor interaction between the phosphorus atom and the nitrogen atom of the dimethylamino group in 4. The oxidation of the trivalent phosphorus atom in 4 and in the related compound 5 by sulfur, selenium, tetrachloro-o-benzoquinone, and hexafluoroacetone led to the corresponding lambda-4P compounds 6-9 and to the lambda-5P compounds 10 and 11. No intramolecular donor-acceptor interaction could be detected in any of these products. There was no reaction between 5 and elemental tellurium. The reaction products were characterized by NMR spectroscopy, mass spectrometry, and by elemental analysis.