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  • 1
    ISSN: 0009-2940
    Keywords: 1,3,5-Trimethylbiuret ; Ethylenediamine, N,N,N′-trimethyl- ; Iron complexes ; Chromium complexes ; Molybdenum complexes ; 1,3,5,2-Triazaphosphorinanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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 PhosphorusSubstitution 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 NMe2 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 Br2 the bromodimethylammonium-bromophosphonium dibromide 7 was formed. The reaction of 4 with Fe2(CO)9 furnished the expected Fe(CO)4 complex 8 while with (C7H8)Cr(CO)4 (C7H8=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 NMe2 group. In the reaction of 4 with C7H8Mo(CO)4 (C7H8=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 NMe2 group. In 10b, the nitrogen atoms of the PN(Me) and of the NMe2 grouping are coordinated to Mo, with formation of a five-membered ring.
    Additional Material: 1 Tab.
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  • 2
    ISSN: 0009-2940
    Keywords: Ethylenediamine, N,N,N′-trimethyl- ; Transition-metal complexes, P - N coordination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-{[2-(Dimethylamino)ethyl]methylamino}-1,3,2-benzodioxaphosphole as a Ligand in Transition-Metal Complexes. Crystal and Molecular Structure of a Tetracarbonyl Chromium DerivativeComplexes of the zerovalent transition metals chromium, molybdenum, iron, and platinum react with the title phosphorus-(III)-compound 3 to give a range of different products: in the coordination compounds 4 and 5, 3 functions as a bidentate ligand, coordinating to the metal through the phosphorus and the nitrogen atom of the dimethylamino group. The structure of 4 was confirmed by a single-crystal X-ray analysis, showing a ligand “bite” angle of 91.0, 91.4° in two independent molecules. In the compounds 7 - 9, involving Mo, Fe, and Pt as a central atom, 3 coordinates solely through P(III). For the platinum(O) complex 9 31P-NMR spectroscopy revealed a dynamic behaviour at room temperature.
    Additional Material: 1 Ill.
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