Verbindungen mit dem 1,3,5,2‐Triazaphosphorinan‐Grundgerüst: Synthese und Koordinationschemie neuartiger, N,N,N ′‐Trimethylethylendiamin‐substituierter Verbindungen mit drei‐und vierfach koordiniertem Phosphor

Compounds with the 1,3,5,2‐Triazaphosphorinane Skeleton: Synthesis and Coordination Chemistry of Novel N,N,N ′‐Trimethylethylenediamine‐Substituted Compounds with Three‐and Four‐Coordinate Phosphorus Substitution of chlorine for the N,N,N ′‐trimethylethylenediamine group in the 1,3,5‐trimethylbiuret derivative 2 produced 4 . The reaction of the 1,3,5,2‐triazaphosphorinane 4 with sulfur furnished the expected P(=S) derivative 5 . Reaction of 4 with methyl iodide led to the formation of the ammonium iodide 6 by methylation of the nitrogen atom of the terminal NMe 2 group while the phosphorus atom of 4 remained unaffected. The structure of 6 was confirmed by a single‐crystal X‐ray structure analysis. In the unusual reaction of 4 with Br 2 the bromodimethylammonium‐bromophosphonium dibromide 7 was formed. The reaction of 4 with Fe 2 (CO) 9 furnished the expected Fe(CO) 4 complex 8 while with (C 7 H 8 )Cr(CO) 4 (C 7 H 8 norbornadiene) 9 was obtained. In 9 , norbornadiene is replaced by one molecule of 4 , which is coordinated by phosphorus and the nitrogen atom of the NMe 2 group. In the reaction of 4 with C 7 H 8 Mo(CO) 4 (C 7 H 8 norbornadiene) the complexes 10a and 10b were formed. In 10a , the P(III) atom of 4 is coordinated to Mo; the second coordination site at Mo(CO) 4 is occupied by the nitrogen atom of the terminal NMe 2 group. In 10b , the nitrogen atoms of the PN(Me) and of the NMe 2 grouping are coordinated to Mo, with formation of a five‐membered ring.