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Synthesis and Structure of σ-Complexes of the Chiral Rhenium Lewis Acid [(η 5 -C 5 H 5 )Re(NO)(PPh 3 )] + and Aromatic Nitrogen Heterocycles

1992; De Gruyter; Volume: 47; Issue: 8 Linguagem: Inglês

10.1515/znb-1992-0820

1865-7117

Michael A. Dewey, D. Andrew Knight, Atta M. Arif, John A. Gladysz,

Metal-Organic Frameworks: Synthesis and Applications

Reactions of (η 5 -C 5 H 5 )Re(NO)(PPh 3 )(OTf) (1) with pyridine, quinoline, and isoquinoline give the respective σ-adducts [(η 5 -C 5 H 5 )Re(NO)(PPh 3 )(NC x H y )] + 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 (CH 3 CH 2 ) 4 N + CN- to give (+)-(S)-(η 5 -C 5 H 5 )Re(NO)(PPh 3 )(CN). The crystal structures of 3 (triclinic, P1̄, a = 9.879(1) A, b = 16.677(2) A, c = 9.962(1) Å, α = 91.477(3)°, β = 99.155(3)°, γ = 100.633(3)°, Ζ = 2) and 4 (triclinic, P1̄, a = 10.961(2) Å, b = 15.770(2) Å, c = 10.159(1) A, a = 87.65(2)°, β = 109.88(2)°, γ = 101.27(2)°, Z = 2) are determined, and the Re—N conformations analyzed.