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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.

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