A NEW SYNTHESIS OF P-SUBSTITUTED YL-1,3,2-LAMBDA(3)-BENZODIAZAPHOSPHORIN-4(1H)-ONES AND ALKYLAMINODIFLUOROPHOSPHANES WITH CHLORODIFLUOROPHOSPHANE - SYNTHESIS AND STRUCTURE OF ETHYL)AMINODIFLUOROPHOSPHANE]DICHLORO)PLATINUM(II)

2,3-Dihydro-3,3-dimethyl-2-oxo-1,3,2 lambda(4)-benzodiazaphosphorin-4( 1H)-one 1 reacted with diethylaminotrimethylsilane to give solely the 2-trimethylsiloxy-lambda(3)-diazaphosphorinone 2. The reaction of 2 wi th the 2-chloro-lambda(3)-diazaphosphorinone 3 yielded the P-O-P-bridg ed compound 4 in an equilibrium reaction with elimination of trimethyl chlorosilane. The synthesis of the P-difluorophosphite-substituted lam bda(3)-benzodiazaphosphorinone 6 was effected by the reaction of chlor odifiuorophosphane (5) with 1 in the presence of triethylamine in a 1: 1 molar ratio, or in the reaction of 5 with 2 or 4. The reaction of 5 with 6 led, with elimination of mu-oxo-bis(difluorophosphane), to the P(III)Cl species 3. 5 reacted with N,N'-dimethylanthranilamide in the presence of triethylamine in a 2:1:2 molar ratio to give the N,N'-bis( difluorophosphane) derivative 9, as evidenced by low temperature (-30 degrees C) F-19- and P-31-NMR data. At room temperature the 2-fluoro-l ambda(3)-diazaphosphorinone 10 was formed from 9 with intramolecular e limination of phosphorus trifluoride. 2-Chloroethyl- or bis(2-chloroet hyl)aminodifluorophosphane 11 and 12 were obtained in the reaction of 5 with 2-chloroethyl- or bis(2-chloroethy)amine hydrochloride in the p resence of triethylamine in a 1:1:2 molar ratio. 12 reacted with (COD) PtCl2 (COD = 1,5-cyclooctadiene) in a 2:1. molar ratio to give the eth yl)aminodifluorophosphane]dichloro}platinum(II) complex 13. The charac terization of 2, 4, 6, and 11-13 is based on their NMR and mass spectr a. The structures of 10 and 13 were established by single-crystal X-ra y analysis. 10 crystallizes with two independent molecules. Both six-m embered heterocycles display an envelope conformation with the phospho rus atoms 36.9 and 50.4 pm, respectively, out of the plane. The phosph orus atoms have pyramidal coordination geometry. The cis-configuration at platinum(II) in the complex 13 was confirmed; two ligands (12) are coordinated to Pt-II via phosphorus. The platinum atom has a distorte d square-planar coordination geometry.