Michael A. Dewey

Synthesis and structure of the rhenium phenylamido complex re(η5-C5H5)(NO)(PPh3)(NHPh); an unprecedented pyramidal amido ligand

In contrast to metal amido complexes that have been structurally characterized to date, the title compound exhibits a pyramidal phenylamido ligand.

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

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, 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.

Syntheses and structures of σ-pyridine, quinoline, and isoquinoline complexes of the formula [(η5-C5H5)Re(NO)(PPh3)(NCxHy)]+ CF3SO3−

Abstract Reaction of (η5-C5H5)Re(NO)(PPh3)(OTf) with pyridine, quinoline, and isoquinoline gives the title complexes in high yields. The crystal structure of the isoquinoline complex is determined, and exhibits unexpected features.