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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

✍ Scribed by Kaukorat, Thomas ;Neda, Ion ;Fischer, Axel ;Jones, Peter G. ;Schmutzler, Reinhard


Book ID
102788127
Publisher
Wiley (John Wiley & Sons)
Year
1993
Tongue
English
Weight
644 KB
Volume
126
Category
Article
ISSN
0009-2940

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✦ Synopsis


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.