Transition-Metal Complexes of the Optically Active Cyclopentadienyl Ligand PinCp*: Crystal Structure of (SRe)-(η5-PinCp*)Re(NO)(PPh3)[CONHCH(CH3)C10H7]
✍ Scribed by Albrecht Salzer; Annegret Hosang; Jutta Knuppertz; Ulli Englert
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- English
- Weight
- 403 KB
- Volume
- 1999
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
The synthesis of (η 5 -PinCp*)Re (CO) 3 [PinCp* = tetra-analysis. By treating the (S Re )-amide with CF 3 CO 2 H and NaBF 4 , (S Re )-(PinCp*)Re(CH 3 )(NO)(PPh 3 ) can be generated. methyl(pinanyl)cyclopentadienyl] is described. Successive substitution of two CO ligands by NO + and PPh 3 generates Protolysis of this compound with HBF 4 /Et 2 O in CD 2 Cl 2 at -78 °C leads to the solvent-stabilized complex (S Re )-[(PinCp* a 1:1 diastereomeric mixture of chiral-at-metal [(S Re )/(R Re )-(PinCp*)Re(CO)(NO)(PPh 3 )]BF 4 . The diastereomers are )Re(NO)(PPh 3 )(ClCD 2 Cl)] + BF 4 -. The thermal and configurational stability of this chiral Lewis acid is converted with sodium methoxide into the derivative "esters" (S Re )/(R Re )-(PinCp*)Re(COOCH 3 )(NO)(PPh 3 ), and investigated at various temperatures. The syntheses of [PinCp*RhCl 2 ] 2 , PinCp*TiCl
3 and PinCp*M(CO) 2 (NO) (M = then with (+)-(R)-(1-naphthylethyl)amine to the "amides" (S Re )/(R Re )-(PinCp*)Re(NO)(PPh 3 )[CONHCH(CH 3 )C 10 H 7 ] Mo, W) are also described. Starting with PinCp* M(CO) 2 (NO), the relatively stable 16-VE complexes PinCp* [(S Re )/(R Re ) = 1:1]. Fractional crystallisation separates the (S Re ) isomer with an optical purity of Ͼ 98%. The latter MCl 2 (NO) and PinCp*W(CH 2 SiMe 3 ) 2 (NO) are synthesized. compound has been characterized by X-ray structure figuration at the stereogenic metal centre up to their de-[ ] Part 7: Ref. [27] [a] Institut für Anorganische Chemie, RWTH Aachen, like PCp used by us before, should serve as an internal chi-D