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  • 1
    ISSN: 0009-2940
    Keywords: Pyrrolidinephosphanes ; 3-Hydroxypyrrolidine ; 3-Diphenylphosphanylpyronlidine ; Salt effects ; Polymorphism ; Homogeneous catalysis ; Palladium ; Asymmetric catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of both enantiomers of 3-diphenylphosphanulpyrrolidiine (2) and several N-substituted derivatives together with two PdIi complexes of this ligand is reported. Form L-malic acid and L-hydroxyproline both enantiomers of 3-hydroxypyrrolidine are prepared without any problems due to epimerization. KPPh2 in the presence of LiCl is shown to be the most effective reagent for the synthesis of 2. The reported X-ray structure determination sof Pdl2 complexes show a rather rigid bicyclic hetero-norbornane skeleton. The flexibility of the other parts of the molecules is obvious in several polymorphs revealed by this method. This polymorphism is additionally investigated by a 31P-CP-MAS study. From solution 1-, 13C- and 31P-NMR studies it is concluded that the bicyclic hetero-norbornane skeleton is retained in solution.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Lewis acids, organometallic ; 14e- Systems ; Allyl complexes ; Rhenium complexes ; Ruthenium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organometallic Lewis Acids, XLVIII[1]. - New Precursors to Organometallic Cationic Lewis Acids with two Accessible Coordination Sites: (OC)4Re(OEt2)FBF3 and (OC)2 (PPh3)2Ru(FBF3)2The allyl transfer reaction between Re(CO)5- and [(η31-allyl)PdCl]2 complexes leads to (allyl)rhenium complexes (η31-H2CCR1CR2R3) Re(CO)4 (1: R1, R2, R3=H; 2; R2, R3=H, R1=Me; 3: R1, R2=H, R3=Me; 4: R1=H, R2, R3=Me). The 2-methylallyl complex 2 has been characterized by low-temperature X-ray diffraction. Protonation of 1 with HBF4 · OEt2 in CH2Cl2 gives the complex (OC)4Re(OEt2)FBF3 (5), which is a precursor for the 14 e- System “(OC)4Re+”. THF and H2O replace the diethyl ether in 5 to give [(OC)4Re(solvent)2]BF4 (6, 7). The reaction of (OC)2(PPh3)2RuCl2 with AgBF4 yields the complex (OC)2 (PPh3)2Ru(FBF3)2 (8), which can be considered as a precursor for the 14 e- cation “(OC)2 (PPh3)2Ru2+” and reacts with H2O to give [(OC)2 (PPh3)2Ru(F)(H2O)]BF4 (9). Complexes 5-9 are characterized by IR, 1H-, 13C-, 31P-and 19F-NMR spectroscopy.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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