Synthesis and Structure of σr-Complexes of the Chiral Rhenium Lewis Acid [(η5-C5H5)Re(NO)(PPh3)]+ and Aromatic Nitrogen Heterocycles Academic Article uri icon

abstract

  • Reactions of (η5-C5H5)Re(NO)(PPh3)(OTf) (1) with pyridine, quinoline, and isoquinoline give the respective σ-adducts [(η5-C5H5)Re(NO)(PPh3)(NCxHy)]+TfO- (2–4) in 86–95% yields. However, 1 and 8-methylquinoline do not react in refluxing xylene (16 h). Reactions of (+)-(R)-1 with quinoline and isoquinoline give (–)-(S)-3 and (+)-(S)-4. Both products form with retention of configuration at rhenium and in >98% ee, as assayed by subsequent reactions with (CH3CH2)4N+CN- to give (+)-(S)-(η5-C5H5)Re(NO)(PPh3)(CN). The crystal structures of 3 (triclinic; P 1, a = 9.879(1) Å, b = 16.677(2) Å, c = 9.962(1) Å, α = 91.477(3)°, β = 99.155(3)°, γ = 100.633(3)°, Z = 2) and 4 (triclinic, P 1, a = 10.961(2) Å, b = 15.770(2) Å, c = 10.159(1) Å, α = 87.65(2)°, β = 109.88(2)°, γ = 101.27(2)°, Z = 2) are determined, and the Re–N conform ations analyzed. © 1992, Walter de Gruyter. All rights reserved.

author list (cited authors)

  • Dewey, M. A., Knight, D. A., Arif, A. M., & Gladysz, J. A.

citation count

  • 12

publication date

  • August 1992