Constitution of Grignard reagent RMgCl in tetrahydrofuran

The constitution of Grignard reagent, RMgCl (R = Me, tBu, Ph or benzyl), was investigated in the solid state by means of X-ray crystallography and in THF by coldspray ionization mass spectrometry (CSI-MS). Three types of crystal structures, (a) [Mg2(mu-Cl3)(THF)6](+)*[RMgCl2(THF)](-), (b) R2Mg4Cl6(THF)6, and (c) [2Mg2(mu-Cl3)(THF)6](+)*[R4Mg2Cl2]2-, were identified, and MeMg2(mu-Cl3)(THF)4-6 were detected as major species of MeMgCl in solution.     

Influence of Mg surface layer for induction period of Grignard reagent formation

Factors that affect the induction period of Grignard reagent formation, which involves heterogeneous reaction between magnesium metal (Mg) and an alkyl halide in ether solvent, has been clarified to achieve safer and more efficient operation in chemical processes. The influence of the Mg surface, especially the effects of carbonate, hydroxide, and oxide layers on the induction period were investigated by measuring the exothermic behavior of Grignard reagent formation by a differential reaction calorimeter. Mg powder was kept in water bubbled with CO₂ or N₂ gas to form a coating on the Mg surface. The calorimetry results for the reaction indicated that both treatments increased the induction period. Thermogravimetric analysis-mass spectrometry was conducted to identify the chemical species and quantify the amount of surface material on the Mg particles. It was found that basic magnesium carbonate and magnesium hydroxide were formed on Mg exposed to CO₂ and N₂, respectively. Subsequent heating the carbonate- or hydroxide-coated Mg at 500 °C caused a MgO layer to form on the surface, which was found to dramatically reduce the induction period.     

Formation and rearrangement of the Grignard reagent from 2-phenylcyclobutylmethyl bromide

Reaction of cis- or trans-2-phenylcyclobutylmethyl bromide with magnesium produces the rearranged 5-phenyl-1-penten-5-ylmagnesium compound 7 in addition to the unrearranged Grignard reagent 6. The former appears to result from very rapid rearrangement of a radical intermediate in the process of Grignard reagent formation. Rearrangement of 6 to 7 also occurs, at a rate which is accelerated by the phenyl group.     

Kumada-Corriu coupling of Grignard reagents,probed with a chiral Grignard reagent

The Grignard reagent 2, in which the magnesium-bearing carbon atom is the sole stereogenic centre has been coupled with vinyl bromide under Pd(0) or Ni(0)-catalysis to give compound 3 with full retention of configuration. Coupling using Fe(acac)3 or Co(acac)2 as catalyst was accompanied by considerable racemisation. These findings are discussed with respect to a dichotomy between concerted polar and stepwise SET transmetallation pathways.     

Effects of water content on magnesium deposition from a Grignard reagent-based tetrahydrofuran electrolyte

It is well known that water causes decomposition of Grignard reagents. When these reagents are used, water or moisture should be eliminated. However, it is possible that a very small amount of water, for example, trapped in the walls of the glassware used, can enter the system even in a well-controlled Ar glove box. Therefore, in this work, the effect of very low concentrations of water on Mg deposition from a Grignard reagent-based electrolyte was studied. It was shown that a minute amount of water, although insufficient to cause destruction of the Grignard reagent, affects the overpotential for Mg deposition, resulting in Mg deposits of different morphology. For reproducible and reversible Mg deposition and dissolution, it is desirable that the water content of the electrolyte is kept as low as possible and the electrolyte is left to stand for at least several hours after preparation.     

Relationships of surface oxygen vacancies with photoluminescence and photocatalytic performance of ZnO nanoparticles

ZnO is one of important semiconductor materials,applied widely in the fields such as the cerams, piezo-electric sensors, catalysts and luminescence apparatus.ZnO nanoparticles not only are ideal materials to pre-pare newly electronic apparatus[1], but als…     

A novel method for the formylation of Grignard reagent

A facile and efficient method for the formylation of Grignard reagent was reported, and a new approach for the preparation of aldehydes from Grignard reagent and benzimida-zolium salts was provided.     

Reactions of a phosphavinyl Grignard reagent with main group mono-halide compounds

The reactions of a phosphavinyl Grignard reagent, [CyPC(Bu^t)MgCl(OEt₂)] Cy=cyclohexyl, with a variety of main group 13, 14 and 16 mono-halide compounds have been investigated. When the Grignard reagent is reacted with bromocatecholborane the terminal phosphavinyl complex, [(C₆H₄O₂)B{C(Bu^t)PCy}], is formed. Related terminal phosphavinyl tin and gallium complexes, [R₃Sn{C(Bu^t)PCy}], R=Me or Buⁿ and [IGa{C(Bu^t)PCy}₂], have been prepared by similar routes. The reaction of the Grignard reagent with PhSeCl has afforded a new λ⁵,λ⁵-diphosphete, [{(Bu^t)CP(Cy)(SePh)}₂], the mechanism of formation of which is discussed. The preparation of a phosphavinyl selenium compound, [(C₈H₄O₂N)PC(Bu^t)(SePh)], is also described. All compounds have been spectroscopically characterised and several have been crystallographically authenticated.     

Superactive and stereospecific catalysts. IV. Influence of structure of esters on MgCl2 supported olefin polymerization catalysts

CH-type catalysts were prepared by reacting MgCl₂ · ROH, where ROH is 2-ethyl hexanol (EH), (R)-2-octanol (R-20), and (S)-2-octanol (S-20), with TiCl₄ in the presence of di-i-butyl phthalate (BP), di-i-butyl terephthalate (BT), (-)-dimenthyl phthalate (MP), or (-)-dimenthyl terephthalate (MT). The MT catalysts were found to incorporate 8.9 to 13% Ti whereas the BP catalysts contain only 1.9 to 2.6% Ti. Comparison of the CH(EH, BP) and CH(EH, MT) catalysts showed that they have about equal number of isospecific active sites per gram of catalyst and the same rate constants of propagation for their nonspecific sites, however, the isospecific sites in the latter are less active by comparison. Consequently, the CH(EH, BP) catalysts is five times more active than the CH(EH, MT) catalysts and produces polypropylene which is 97% isotactic (reflux n-heptane insoluble) as compared to 84.7% for the latter. The catalysts derived from 2-octanols are much less active than the corresponding catalysts prepared with 2-ethyl hexanol due to lack of reactivity with phthalic anhydride which permits excessive incorporation of TiCl₄ to form nonstereospecific catalytic sites as well as inactive Ti species.     

Cationic copolymerization of tetrahydrofuran with epoxides. III. Synthesis of block copolymers

Polymerization of various cyclic ethers by BF₃·O(C₂H₅)₂ in the presence of polymeric glycol leads to the formation of hydroxyl terminated block copolymers. Where poly(oxyethylene glycol) is used as the polymeric glycol, fission of the poly(oxyethylene glycol) chain occurs, and block copolymers, containing shorter ethylene oxide unit sequences are obtained. With poly(oxypropylene glycol), on the other hand, the polymer chain remains intact. This may be due to the steric influence of the pendant methyl groups. The cyclic oligomers formed as by-products in the polymerizations are easily removed.     

The cationic cluster Grignard [{MgCl(thf)2}3(mu3-C3H5)2]+

The synthesis and structure of [{MgCl(thf)2}3(mu3-C3H5)2]2[Mg(C3H5)4], which contains both a cationic cluster Grignard and a tetraorganomagnesiate dianion, are reported.