Synthesis, optical resolution, and absolute configuration of pseudotetrahedral organorhenium complexes (.eta.-C5H5)Re(NO)(PPh3)(X) Academic Article uri icon

abstract

  • Reaction of [(η-C6H5)Re(NO)(PPh3)(CO)]+BF4− (1) with CH3ONa/CH3OH affords the ∜ester∝ (η-C5H5)Re(NO)(PPh3)(COOCH3) (2). Reaction of 2 with (−)-(S)-α-(1-naphthyl)ethylamine or (+)-(R)-α-(1-naphthyl)ethylamine gives ∜amide∝ (η-C5H5)Re(NO)(PPh3)(CONHCH(CH3)C10H7) (8). The diastereomers of 8 are separated by benzene/hexane recrystallization; (−)-(RS)-8 and (+)-(SR)-8 are least soluble. These are treated with CF3CO2H and NaBF4 to give (−)-(R)-1 and (+)-(S)-1, respectively. Resolved 1 is then used to prepare optically active 2, (η-C5H5)Re(NO)(PPh3)(CH3) (3), [(η,-C5H5)Re(NO)(PPh3)(=CH2)]+PF6− (4), (η-C5H5)Re(NO)(PPh3)(CH2C6H5) (9), (η-C5H6)Re(NO)(PPh3)(CH2CH3) (10), and (η,-C5H5)Re(NO)-(PPh3)(CHO) (11) via known procedures. An X-ray crystal structure of (−)-(R)-9 (space group P212121, a = 12.874 (5) Å, b = 11.889 (3) Å, c = 16.077 (7) Å, Z = 4, R = 0.034) establishes the absolute configurations of resolved 1–4 and 8–11. Also described are the following: ORD and CD spectra; several unsuccessful resolution attempts; the synthesis of [(η-C5H5)Re(NO)(PPh3)(CH2P+Ph2(O-l-menthyl))]+PF6+ (7) (used as an optical purity assay); comparisons with isostructural chiral organometallic complexes. © 1982, American Chemical Society. All rights reserved.

author list (cited authors)

  • Merrifield, J. H., Strouse, C. E., & Gladysz, J. A.

citation count

  • 52

publication date

  • September 1982