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  • Ethylenediamine, N,N,N′-trimethyl-  (2)
  • Supramolecular chemistry  (2)
  • 1,3,2λ5-Diazaphosphetidin-4-ones,2-chloro-2-phenyl-2-(p-tolylthio)-1,3-diorgano-  (1)
  • 1
    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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  • 2
    ISSN: 0009-2940
    Keywords: Calix[4]arenes ; Supramolecular chemistry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparation of Phosphorus -  and Fluorine-Containing Calix[4]arene Derivatives. Conformational Analysis, Separation of the Conformers, and X-Ray Crystal Structure Analysis of a Cone ConformerHerrn Professor Helmut Werner zum 60. Geburtstag gewidmet.The Calix[4]arene 1 reacts with hexamethyldisilazane or (diethylamino)trimethylsilane to form the bis-trimethylsilyl-ated derivative 2. Treatment of 2 with PF2C1 gives the mono-and bis-difluorophosphites 3 and 4, which react with elimination of Me3SiF or PF3 to yield the monofluorophosphite derivative 5. All four OH hydrogen atoms in 1 are replaced by lithium on reaction with nBuLi with formation of the tetrali-thiated product 6. This has been allowed to react with the Pchlorophosphorinanones 7-9. From 7 the cone conformer 10a is formed, whereas in the case of 8 and 9 a mixture of all four possible conformars 11a-d and 12a-d is obtained. The pure conformers 12a-d are isolated. By refluxing the cone conformer 12a in tetrachloroethane a conformational conversion is effected. In order to evaluate its coordinating ability, 12a was allowed to react with dichloro(cycloocta-1, 5-diene)platinum(II) to form the trans-disubstituted complex 13. In the case of 12a (acetonitrile solvate) a single-crystal X-ray structure analysis has been conducted. The molecule displays a cone conformation, whereby two of the opposing phenyl rings are approximately parallel and the other two approximately perpendicular to each other.
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  • 3
    ISSN: 0009-2940
    Keywords: Calix[4]resorcinols ; Dioxaphosphocins ; Supramolecular chemistry ; Solid-state NMR spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterisation of the reactive tetrakis (O,O-phosphorus)-Bridged calix[4]resorcinols 3 and 4 is described. Because of its poor solubility in common organic solvents, a solid-state NMR investigation of 3 (1H, 13C, 31P) was conducted. Reaction of 3 with MeMgl, Me3 SiMNe2, and HNMe2 furnished the η3γ3P-substituted cavitands 5 and 6. Oxidative addition reactions of 6 with the (H2N)2C(=O)/H2O2 (1:1) adduct, tetrachloro-o-benzoquinone (TOB), and hexafluoroacetone (HFA) led to the η4γ5P derivative 7, and to the η5γ5P derivatives 8 and 9. An X-ray crystal-structure determination of the tetrakis(O,O-phosphorus)-bridged calix[4]resorcinol 4 has been conduced. The framework displays the cone conformation; the chlorine atoms are directed inwards.
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  • 4
    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.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 1395-1397 
    ISSN: 0009-2940
    Keywords: 1,3,2λ5-Diazaphosphetidin-4-ones,2-chloro-2-phenyl-2-(p-tolylthio)-1,3-diorgano- ; Phosphorus, pentacoordinated ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea (1) or N-methyl-N′-phenyl-N,N′-bis(trimethylsilyl)urea (2) with p-toluenesulfenyl chloride furnished N,N′-dimethyl-N-(p-tolylthio)-N′-
    Additional Material: 1 Ill.
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