- The coordination modes of simple diarylmagnesium species: some representative X-ray crystal structures
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The coordination modes of simple diarylmagnesium species have been investigated by crystal structure studies of representation compounds.In the case of diphenylmagnesium (1), both the solvated monomeric complex Ph2Mg*2 (1a) and the solvent-free compo
- Markies, Peter R.,Schat, Gerrit,Akkerman, Otto S.,Bickelhaupt, Friedrich,Smeets, Wilberth J.J.,et al.
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- In Quest of the Double Rotaxane Formation of the Bis(coronand) (1,5),(2,4)-Durenetetrayl-bis(18-crown-5) with Organomagnesium Compounds
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The interaction between the title compound, bis(coronand) 8, and the diarylmagnesium compounds Ph2Mg and (p-tBuC6H 4)2Mg in diethyl ether leads to the formation of 1:2 complexes (9 and 10, respectively), irrespe
- Van Klink, Gerard P. M.,Nomoto, Tateo,Lutz, Martin,Spek, Anthony L.,Akkerman, Otto S.,Bickelhaupt, Friedrich
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- Magnesiation of Aryl Fluorides Catalyzed by a Rhodium-Aluminum Complex
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We report the magnesiation of aryl fluorides catalyzed by an Al-Rh heterobimetallic complex. We show that the complex is highly reactive to cleave the C-F bonds across the polarized Al-Rh bond under mild conditions. The reaction allows the use of an easy-to-handle magnesium powder to generate a range of arylmagnesium reagents from aryl fluorides, which are conventionally inert to such metalation compared with other aryl halides.
- Fujii, Ikuya,Semba, Kazuhiko,Li, Qiao-Zhi,Sakaki, Shigeyoshi,Nakao, Yoshiaki
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supporting information
p. 11647 - 11652
(2020/08/06)
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- PROCESS FOR PRODUCING OPTICALLY ACTIVE ALCOHOL
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Disclosed is a method for producing an optically active alcohol including reacting a titanium compound, an aromatic magnesium compound and a carbonyl compound in the presence of an optically active biphenol compound having a predetermined structure and an ether compound having a predetermined structure.
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Page/Page column 20
(2012/02/14)
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- Grignard reaction with chlorosilanes in THF: A kinetic study
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Kinetics of the reactions of phenylmagnesium chloride and bromide and diphenylmagnesium with chlorosilanes were investigated in tetrahydrofurane (THF) and in THF-hydrocarbon mixtures. The reaction in THF is much faster than that in diethyl ether. Assuming coordination of magnesium halides with three molecules of THF, concentrations of all the species involved in Schlenk equilibrium were calculated. In the Grignard reaction, species R2Mg and RMgX react competitively accompanied by additional reaction paths involving electrophilic catalysis by magnesium halide. This conclusion also proved to be valid for the Grignard reaction with a ketone and probably can be expanded to any Grignard reaction. When Schlenk equilibrium is shifted far to the RMgX species, the catalytic pathways are insignificant. Substituents at the silicon center control the rate of the reaction through their inductive and steric effects.
- Tuulmets, Ants,Nguyen, Binh T.,Panov, Dmitri
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p. 5071 - 5076
(2007/10/03)
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- Method for producing alkyl-bridged ligand systems and transition metal compounds
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The invention relates to a method for producing highly substituted alkyl-bridged ligand systems on the basis of indene derivatives and transition metal compounds. Said alkyl-bridged ligand systems can be obtained in high yields using this method.
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- Intramolecularly coordinated arylmagnesium compounds: effects on the Schlenk equilibrium
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A series of phenylmagnesium bromides (1, 3-8) with ortho-substituents capable of forming intramolecular coordinative bonds along with the corresponding diarylmagnesium compounds (1a, 3a-6a, 8a) have been synthesized.The thermodynamic parameters ΔHs and ΔSs for the Schlenk equilibria (2 ArMgBr Ar2Mg + MgBr2) have been determined by variable temperature NMR spectroscopy.Crystal structures were obtained of 5,6,8,9-tetrahydrodibenzoxamagnesecin (2a) and bis(2,6-di(methoxymethyl)phenyl)magnesium (4a).The extent of intramolecular coordination in these compounds as determined in the solid state, is used in the discussion of the influence of substituents on the Schlenk equilibrium parameters.Unusual penta- or hexa-coordination is encountered and explained as a consequence of intramolecular coordination.
- Markies, Peter R.,Altink, Rinke M.,Villena, Alan,Akkerman, Otto S.,Bickelhaupt, Friedrich,et al.
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p. 289 - 312
(2007/10/02)
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- PREPARATION OF SOLVATED AND/OR UNSOLVATED SIMPLE AND MIXED DIARYLMAGNESIUMS
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Arylation of arylmagnesium halide etherates by aryllithium provides a convenient method of preparing ar2Mg(Et2O)2 or Ar2Mg(THF)2.The ether complexes can be completely desolvated but the THF complexes cannot.Mixed diarylmagnesium tetrahydrofuranates, Ar1Ar2Mg(THF)2, although coordinationally saturated, have 1H and 13C NMR spectra which suggest that they are fluxional.
- Screttas, Constantinos G.,Micha-Screttas, Maria
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p. 325 - 334
(2007/10/02)
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