ISSN:
0009-2940
Keywords:
2,3-Dihydro-1,3-dimethyl-1,3,2-benzodiazaphosphorin-4-(1H)-ones, 2-trimethylsiloxy-, 2-oxo-, and 2-fluoro-substituted
;
Equilibrium reaction
;
Aminodifluorophosphanes
;
Platinum complex
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
2,3-Dihydro-1,3-dimethyl-2-oxo-1,3,2δ4-benzodiazaphosphorin-4(1H)-one 1 reacted with diethylaminotrimethylsilane to give solely the 2-trimethylsiloxy-δ3-diazaphosphorinone 2. The reaction of 2 with the 2-chloro-δ3-diazaphosphorinone 3 yielded the P - O - P-bridged compound 4 in an equilibrium reaction with elimination of trimethylchlorosilane. The synthesis of the P-difluorophosphite-substituted δ3-benzodiaza-phosphorinone 6 was effected by the reaction of chlorodifluorophosphane (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 μ-oxo-bis(difluoro-phosphane), 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°C) 19F-and 31P-NMR data. At room temperature the 2-fluoro-δ3-diazaphosphorinone 10 was formed from 9 with intramolecular elimination of phosphorus trifluoride. 2-Chloroethyl- or bis(2-chloroethyl)aminodifluorophosphane 11 and 12 were obtained in the reaction of 5 with 2-chloroethyl- or bis(2-chloroethyl)amine hydrochloride in the presence 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 {cis-bis[bis(2-chloroethyl)aminodifluorophosphane]dichloro}platinum(II) complex 13. The characterization of 2, 4, 6, and 11-13 is based on their NMR and mass spectra. The structures of 10 and 13 were established by single-crystal X-ray analysis. 10 crystallizes with two independent molecules. Both six-membered heterocycles display an envelope conformation with the phosphorus atoms 36.9 and 50.4 pm, respectively, out of the plane. The phosphorus atoms have pyramidal coordination geometry. The cis-configuration at platinum(II) in the complex 13 was confirmed; two ligands (12) are coordinated to PtII via phosphorus. The platinum atom has a distorted square-planar coordination geometry.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19951280707
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