Equimolar solvate

Equation [9.91e] developed for the ideal solution E-A-B permits us to establish the relationship between the eomposition of mixed solvent Xg and the solvate shell eomposition Xg. For the speeialease of equimolar solvates, the expressionofresolvationeonstant is written in the form ... 

Alkenes are scavengers that are able to differentiate between carbenes (cycloaddition) and carbocations (electrophilic addition). The reactions of phenyl-carbene (117) with equimolar mixtures of methanol and alkenes afforded phenylcyclopropanes (120) and benzyl methyl ether (121) as the major products (Scheme 24).51 Electrophilic addition of the benzyl cation (118) to alkenes, leading to 122 and 123 by way of 119, was a minor route (ca. 6%). Isobutene and enol ethers gave similar results. The overall contribution of 118 must be more than 6% as (part of) the ether 121 also originates from 118. Alcohols and enol ethers react with diarylcarbenium ions at about the same rates (ca. 109 M-1 s-1), somewhat faster than alkenes (ca. 108 M-1 s-1).52 By extrapolation, diffusion-controlled rates and indiscriminate reactions are expected for the free (solvated) benzyl cation (118). In support of this notion, the product distributions in Scheme 24 only respond slightly to the nature of the n bond (alkene vs. enol ether). The formation of free benzyl cations from phenylcarbene and methanol is thus estimated to be in the range of 10-15%. However, the major route to the benzyl ether 121, whether by ion-pair collapse or by way of an ylide, cannot be identified. 

Fig. 39. Selective adsorption to a polymer chain from a bulk solvent medium comprising an equimolar mixture of liquid 1 and liquid 3. Only molecules of liquid 1 (circled) in excess of the equimolar ratio in the solvated shell are part of the selective adsorption complex131)...

The donor number, DN, of a solvent, proposed by Gutmann, is a measure of the Lewis basicity of the solvent, i.e. its ability to donate a pair of electrons [16]. The DN is determined by measuring the negative enthalpy for the reaction of equimolar quantities of the solvent with the standard Lewis acid, SbCls, at room temperature in 1,2-dichloroethane (Scheme 1.1), and reflects the ability of the solvent to solvate Lewis acids. SbCls reacts with protic solvents such as alcohols... 

It has been noted above that the weakly solvated cation [Rh(diphos)(MeOH)2]+ can be obtained by hydrogenation of [Rh(diphos)(C7Hs)][BF4]. If the former compound is allowed to react with an equimolar quantity of [IrH5(PPrj)2] the di-p-hydrido complex (140) is formed (equation 330). The presence of base merely increases the yield. Only the heavy atoms have been located by X-ray crystallography.1347... 

Similarly MeCdCl, obtained from equimolar Mc2Cd and CdCl2 in dimethylsulfox-ide (DMSO) and not isolated either in the solvated form or as a preformed complex, ... 

The CRM reaction took an appreciably different course when solvated starting materials were used. Only one Cp exchange at the lanthanide center was observed. When KCp was reacted with LnCp3(THF) in excess or in three times more than the equimolar ratio, no Cp ring transfer to the lanthanum center was observed (Scheme 96).463... 

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