Benzene, hexamethylbenzene, and pentamethylcyclopentadienyl chiral half-sandwich complexes of ruthenium(II).

摘要

The equilibrium diastereomeric mixture of (S_Ru,R_C)- and (R_Ru,R_C)-(η6-C₆H ₆) (1a,a′) underwent chloride substitution reactions with the pseudohalide ions azide, cyanate, thiocyanate, and nitrite to form equilibrium mixtures of the corresponding azido (2a,a ′), isocyanato (3a,a′), isothiocyanato (4a,a′), thiocyanato ( 4b), nitro (5a), and nitrito (5b) analogs, respectively. These complexes are epimeric at ruthenium in room-temperature solutions. The equilibrium mixtures were characterized at room temperature by combination of 1H and 13C{lcub}1H{rcub} NMR spectroscopy, UV-Visible spectroscopy, circular dichroism, and infrared spectroscopy. The major diastereomers/isomers were characterized by single-crystal X-ray crystallography (2a–5a) and low-temperature 1H NMR spectroscopy (2a–4a).; Reaction of the complexes (η6-C₆Me ₆)Cl₂Ru(PR₃), 6, [PR₃ = DPVP (diphenylvinylphosphine) (a), PMe₃ ( b), PPh₃ (c)] with NaPF₆ in acetonitrile gave the cationic complexes [(η6-C₆Me₆ )ClRu(PR₃)(NCCH₃)]PF₆, 7a–c . Reaction of complexes 6a–c and 7a–c with HC≡CSiMe₃ and HC≡CPh (and NaPF₆ for 6a–c) in MeOH gave the carbene complexes [(η 6-C₆Me₆)Cl(PR₃)Ru=C(OCH₃)CH ₃]PF₆, 8a–c, and [(η6-C ₆Me₆)Cl(PR₃)Ru=C(OCH₃)CH₂Ph]PF ₆, 9a–c, respectively. The solid state structures and the solution dynamic behavior of 8a–c and 9a–c are discussed. Reaction of complex 7a with HC≡CCH ₂CH₂OH in McOH gave the complex [(η6-C ₆Me₆)Cl(DPVP)-Ru=, 10. Reaction of 6a (and NaPF₆) and 7a with HC≡CC(OH)Ph₂ in McOH gave the novel phosphorus-ylide complex [(η6-C₆Me₆)Cl-, 11. With dimethylpropargylamine in CH₂Cl ₂ or dichloroethane, 6a (and NaPF₆) and 7a gave the complex [(η6-C₆Me₆)Cl(DPVP)-Ru{lcub}=, 12, and the metallacyclic complex [(η6-C ₆Me₆)Cl-, 13. In the absence of MeOH, reaction of 7a with HC≡CC(OH)Ph₂ or HC≡C