Optically active transition-metal complexes, 8 -: Transition-metal complexes of the optically active cyclopentadienyl ligand PinCp:: Crystal structure of (SRe)-(η5-PinCp)Re(NO)(PPh3)[CONHCH(CH3)C10H7]

被引：0

作者：

Salzer, A ^{[1
]}

Hosang, A ^{[1
]}

Knuppertz, J ^{[1
]}

Englert, U ^{[1
]}

机构：

[1] Rhein Westfal TH Aachen, Inst Anorgan Chem, D-52056 Aachen, Germany

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 1999年 / 09期

关键词：

half-sandwich complexes; molybdenum; optically active complexes; rhenium; tungsten;

D O I：

暂无

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis of (eta(5)-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 [(S-Re)/(R-Re)- (PinCp*)Re(CO)(NO)(PPh3)]BF4. The diastereomers are converted with sodium methoxide into the derivative "esters" (S-Re)/(R-Re)-(PinCP*)Re(COOCH3)(NO)(PPh3), and then with (+)-(R)-(1-naphthylethyl)amine to the "amides" (S-Re)/(R-Re)-(PinCp*)Re(NO)(PPh3)[CONHCH(CH3)C10H7] [(S-Re)/(R-Re) = 1:1] Fractional crystallisation separates the (S-Re) isomer with an optical purity of > 98%. The latter compound has been characterized by X-ray structure analysis. By treating the (S-Re)-amide with CF3CO2H and NaBF4, (S-Re)-(PinCp*)Re(CH3)(NO)(PPh3) can be generated. Protolysis of this compound with HBF4/Et2O in CD2Cl2 at -78 degrees C leads to the solvent-stabilized complex (S-Re)-[(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.

引用

页码：1497 / 1505

页数：9

共 29 条

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Optically active transition-metal complexes, 8 -: Transition-metal complexes of the optically active cyclopentadienyl ligand PinCp*:: Crystal structure of (SRe)-(η5-PinCp*)Re(NO)(PPh3)[CONHCH(CH3)C10H7]

Optically active transition-metal complexes, 8 -: Transition-metal complexes of the optically active cyclopentadienyl ligand PinCp:: Crystal structure of (SRe)-(η5-PinCp)Re(NO)(PPh3)[CONHCH(CH3)C10H7]