VERBINDUNGEN MIT DEM 1,3,2- BENZODIAZAPHOSPHORINAN-4-ON GRUNDGERÜST: SYNTHESE VON NEUARTIGEN N,N′,N′- TRIMETHYLETHYLENDIAMINSUBSTITUIERTEN DERIVATEN MIT DREI- UND VIERFACH KOORDINIERTEM PHOSPHOR

Abstract

The reaction of N,N′-dimethylanthranilic amide with phosphorus trichloride furnished 3, the first compound of P(III), involving the 1,3,2-benzodiazaphosphorinanone ring system. In the reaction of 3 with N-trimethylsilyl-N,N′,N′-trimethylethylenediamine 2 the product 4 was formed. The possibility of in tramolecular donor-acceptor-interaction between the nitrogen atom of the (CH₃)₂N group and the λ³P atom was investigated by ¹H n.m.r. studies. No interaction was observed. Oxidative addition of elemental sulfur at the λ³P atom of 4 gave the λ⁴P-thiophosphoryl compound 5 while the reaction of 4 with methyl iodide and bromine, in an unusual reaction, furnished the ammonium salts 6 and 7. The N-Br bond in 7 was established by IR-spectroscopy. In the reaction of 4 with C₇H₈Cr(C0)₄ (C₇H″ = norbornadiene) a substitution product 8, involving intramolecular coordination of 4 to Cr(O) via λ³P and the nitrogen atom of the (CH₃)₂N grouping was formed. By contrast, the reaction of C₇11₈Mo(CO)₃ (C₇H₈ = cycloheptatriene) with 4 (= L) yielded the complex L₃Mo(CO), 9 in which three ligands 4 are coordinated to Mo(O) via the λ³P atom only.

Key Words:

• 1,3,2-Benzodiazaphosphorinan-4 one
• N,N′,N′-trimethylethylenediamine
• intramolecular interactions
• coordination compounds
• ammonium salt
• phosphonium salt.