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  • Rhenium  (1)
  • phosphorus ligands  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Nucleophilic Addition of Secondary Phosphines to Cationic Dienyl Tricarbonyliron Complexes: A novel Route to Optically Active PhosphinesOptically Active Transition Metal Complexes, Part 6. Part 5: U. Englert, M. Käser, A. Salzer, Inorg. Chem. 1995, 34, 6231-6232. (1996)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 523-528 
    Details
    ISSN: 0947-6539
    Keywords: carbonyl complexes ; chiral ligands ; iron complexes ; phosphorus ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Secondary phosphines such as HPPh2 and to the cationic iron dienyl complex [η5-(1R)-ethylnopadienyl)Fe-(CO)3]+ (1) by nucleophilic addition. The phosphonium salt initially formed is readily deprotonated to yield an optically active tertiary phosphine [(n4-(1 R)-ethylnopadienePPh2)Fe(CO)3] (2b). A similar reaction also occurs with [C6H7Fe-(CO)3]+ (3) and [C7H9Fe(CO)3]+ (4) to give [(C6H7PPh2)Fe(CO)3] (5) and [(C7H9PPh2)Fe(CO)3] (6) in good yields. The mechanism of formation of these novel phosphines is discussed. Complex 2 b crystallizes in the space group P212121 (no. 19); 5 crystallizes in the space group P21/c (no. 14). Like other monodentate optically active phosphines, 2 b is capable of coordinating to transition metal complexes. It forms palladium complexes on reaction with [{μ-chloro(allyl)palladium}2] as well as with [{μ-chloro[(N,N-dimethylamino-kN-2-methyl)phenyl-kC]palladium}2] (11). The latter reaction product crystallizes in the space group P31 (no. 144).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19960020511
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  • 2
    Electronic Resource
    Electronic Resource
    Transition-Metal Complexes of the Optically Active Cyclopentadienyl Ligand PinCp*: Crystal Structure of (SRe)-(η5-PinCp*)Re(NO)(PPh3)[CONHCH(CH3)C10H7] (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1497-1505 
    Details
    ISSN: 1434-1948
    Keywords: Half-sandwich complexes ; Molybdenum ; Optically active complexes ; Rhenium ; Tungsten ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of (η5-PinCp*)Re(CO)3 [PinCp* = tetramethyl(pinanyl)cyclopentadienyl] is described. Successive substitution of two CO ligands by NO+ and PPh3 generates a 1:1 diastereomeric mixture of chiral-at-metal [(SRe)/(RRe)-(PinCp*)Re(CO)(NO)(PPh3)]BF4. The diastereomers are converted with sodium methoxide into the derivative “esters” (SRe)/(RRe)-(PinCp*)Re(COOCH3)(NO)(PPh3), and then with (+)-(R)-(1-naphthylethyl)amine to the “amides” (SRe)/(RRe)-(PinCp*)Re(NO)(PPh3)[CONHCH(CH3)C10H7] [(SRe)/(RRe) = 1:1]. Fractional crystallisation separates the (SRe) isomer with an optical purity of 〉 98%. The latter compound has been characterized by X-ray structure analysis. By treating the (SRe)-amide with CF3CO2H and NaBF4, (SRe)-(PinCp*)Re(CH3)(NO)(PPh3) can be generated. Protolysis of this compound with HBF4/Et2O in CD2Cl2 at -78 °C leads to the solvent-stabilized complex (SRe)-[(PinCp*)Re(NO)(PPh3)(ClCD2Cl)]+BF4-. The thermal and configurational stability of this chiral Lewis acid is investigated at various temperatures. The syntheses of [PinCp*RhCl2]2, PinCp*TiCl3 and PinCp*M(CO)2(NO) (M = Mo, W) are also described. Starting with PinCp*M(CO)2(NO), the relatively stable 16-VE complexes PinCp*MCl2(NO) and PinCp*W(CH2SiMe3)2(NO) are synthesized.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
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