Synthesis, Characterization, and PGSE (1H and 19F) NMR Diffusion Studies on Cationic (η6- Arene)Mn(CO)3+ Complexes: Boron Counterion, Ion Pairing, and Solvent Dependences
摘要:
The synthesis, characterization, and PGSE (H-1 and F-19) NMR diffusion studies on the cationic [(eta(6)-arene)Mn-(CO)(3)][X] (arene = anisole, 4-chloroanisole, and 1,3,5-trimethoxybenzene; X = BPh4 and BArF) are reported. The tetraphenyl borate complexes of anisole and 4-chloroanisole show surprisingly strong ion pairing in dichloromethane solution, whereas the BArF salts do not. H-1,H-1-NOESY data support this anion selectivity. In chloroform solution one finds the usual strong ion pairing for both anions. The solid-state structure of [(eta(6)-1,3,5-trimethoxybenzene)-Mn(CO)(3)][BPh4] has been determined. C-13 NMR and IR data for the new complexes are reported. The observed IR frequencies are higher for the BArF complexes than for the BPh4 complexes.
Ferrocenyl-Substituted (η<sup>5</sup>-Hydroxyalkylcyclohexadienyl)tricarbonylmanganese Complexes: Synthesis, Structural Determinations, and Formation of Carbenium Ions
作者:Antoine Eloi、Mael Poizat、Albin Hautecoeur、Armen Panossian、Françoise Rose-Munch、Eric Rose
DOI:10.1021/om200905p
日期:2011.11.14
Ferrocenyl-substituted (η5-hydroxyalkylcyclohexadienyl)tricarbonylmanganesecomplexes have been synthesized as well as the corresponding carbenium dinuclear complexes after dehydroxylation. Studies in solution and in the solid state of these zwitterionic species show not only the electronic influence of the positive charge on the η5-Mn complex but also the participation of the two metal atoms in the
Preparation and reactivity of ν6-veratrolemanganese tricarbonyl tetrafluoroborate
作者:A.J. Pearson、I.C. Richards
DOI:10.1016/s0022-328x(00)99267-2
日期:1983.11
Reaction of pentacarbonylmanganese tetrafluoroborate with veratrole (1,2-dimethoxybenzene) affords η6-veratrolemanganese tricarbonyl tetrafluoroborate in 66% yields. This complex does not react satisfactorily with alkyllithium compounds, but it does undergo highly regioselective reaction with the lithium enolate of cyclohexanone, ortho to the MeO substituent. The product was converted to 2-(2,3-di