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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1091-1100 
    ISSN: 0009-2940
    Keywords: 3,4-Bis(phosphanyl)pyrrolidines ; Palladium complexes ; Rhodium complexes ; Asymmetric hydrogenation ; Phosphanes, chiral ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantioselective Catalysis, IX[1]. - New Optically Pure 3,4-Bis(phosphanyl)pyrrolidines with Phenyl and Anisyl Groups Including Their Palladium and Rhodium ComplexesMethods for the synthesis of the diastereomeric mixture of the [P(R,S),3R,4R,P′(R,S)]1-1-(tert1-butoxycarbonyl)1-3,4-bis[(2-methoxyphenyl)phenylphosphanyl]pyrrolidines (2a, b, c) are described. For the chromatographic separation and purification of the ligand diastereomers we transformed them into the PdI21-complexes (10a, b, c). The structure of (PR,3R,4R,P′R)1-1-(tert1-butoxycarbonyl)1-3,4-bis[(2-methoxyphenyl)phenylphosphanyl]pyrrolidine-P,P′}diiodopalladium (10 b) was determined by X-ray diffraction. Treatment of the palladium complexes with KCN yielded the pure phosphanes. The rhodium complexes (11a, 11b, 11c), which can be used as catalysts in enantioselective hydrogenations, were obtained by reaction of [Rh(COD)2]BF4 with compound 2a, 2b, or 2c.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: 3,4-Bis(phosphanyl)pyrrolidines ; Palladium complexes ; Rhodium complexes ; Asymmetric hydrogenation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantioselective Catalysis, VIII[1]. - New 1,2-Bisphosphane Ligands with Four Stereogenic Centers and Additional Methoxy Groups for Asymmetric Catalytic Hydrogenation*The synthesis of N-acyl derivatives of all possible diastereomers of [P(R,S), 3R, 4R,P′(R,S)]-3,4-bis[(benzyl)phenylphosphanyl]-pyrrolidine and [P(R,S), 3R, 4R,P′(R,S)]-3,4-bis[(2-methoxybenzyl)phenylphosphanyl]pyrrolidine in optical pure form is described. Palladium and rhodium complexes with these ligands were prepared. The enantioselective hydrogenation of acetamidocinnamic acid with these rhodium complexes was studied at H2 pressures between 1 and 75 bar. There is only a small influence of the 2-methoxy group in the ligand on the catalytic hydrogenation when compared with the respective unsubstituted diastereomer. The structure of {[PR,3R, 4R,P′R)-1-(tert-butoxycarbonyl)-3,4-bis[(2-methoxybenzyl)phenylphosphanyl]pyrrolidine-P,P′}diiodopalladium was determined by X-ray diffraction.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0009-2940
    Keywords: Isocyanide complexes / γ-Oxoisocyanide complexes / Cyano complexes of iron (II), ruthenium(II), palladium(II), platinum(II) ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pseudohalogeno Metal Compounds, LXXIII. - γ-Oxoisocyanide Complexes of Iron(II), Ruthenium(II), Palladium(II), and Platinum(I1) from Cyano Complexes and α,β-Unsaturated Carbonyl Compounds in the Presence of Et2O - HBF+ Crystal Structure of cis-(phen)2Fe[CNC(CH3)2CH2C(O)CH=C(CH3)2]2+2(BF-4)2Reactions of trans-(R3P)2M(CN)2 (M = Pd, Pt), cis-[(phen)2-Fe(CN)2], Cp(dppe)Fe(CN), and Cp(Ph3P)2Ru(CN) with several α,β-unsaturated ketones in the presence of Et2O-HBF4 yield complexes containing the γ-oxoisocyanide ligand: trans [R3P)2M(CN-CR1R2-C(O)R4)2]2+(BF4-)2 (5-8), trans -[(R3P)2Pt(CN)(CN-CR1R2-CHR3-C(O)R4)]+ BF4- (9), cis [(phen2)]Fe(CN-CR1R2-CHR3-C(O)R4)2]2+(BF4-)2 (10), and [CpL2M(CN-CR1R2-CHR3-C(O)R4)]*BF4- (11, 12) (M = Fe, Ru; L = PPh3, 1/2 dppe). The compounds were characterized by their spectroscopic data, 10g by X-ray crystallography. The carbonyl function of the coordinated ligands could be reduced by NaBH4/CeCl3·6H2O in some cases to give complexes of γ-hydroxyisocyanide and oxazine-2-ylidene ligands.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    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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