Formation reaction table

Solution Table 7.2 gives AHp for styrene at 298.15K. The formation reaction is... 

Much of the early work into the rhodium(II)-catalysed formation of oxazoles from diazocarbonyl compounds was pioneered by the group of Helquist. They first reported, in 1986, the rhodium(II) acetate catalysed reaction of dimethyl diazomalonate with nitriles.<86TL5559, 93T5445, 960S(74)229> A range of nitriles was screened, including aromatic, alkyl and vinyl derivatives with unsaturated nitriles, cyclopropanation was found to be a competing reaction (Table 3). 

The adsorption energy of N2 is also low, but that of NO on the (100) surface is substantial. Notwithstanding the very similar activation energies for N2 and NO formation (see Tables 1.4 and 1.5), the strong interaction of NO with both surfaces implies that the selectivity of the reaction toward N2 will be high at low temperatures. The NO once formed will not desorb and can only be removed as N2O. 

Note that we have written two defect reactions for the case of vacancy formation in Table 3-2. Pyrophosphate is an insulator and the formation of a positively-charged vacancy is much less likely than the vacancy plus a free positive charge. This brings us to a rule found in defect chemistry that seems to be universal, namely ... 

The thermodynamic stability of a complex ML formed from an acceptor metal ion M and ligand groups L may be approached in two different but related ways. (The difference between the two approaches lies in the way in which the formation reaction is presented.) Consistent with preceding sections, an equilibrium constant may be written for the formation reaction. This is the formation constant Kv In a simple approach, the effects of the solvent and ionic charges may be ignored. A stepwise representation of the reaction enables a series of stepwise formation constants to be written (Table 3.5). 

Sultam 53 has proved to be an excellent chiral auxiliary in various asymmetric C-C bond formation reactions. One more example of using sultam 53 is the asymmetric induction of copper(I) chloride-catalyzed 1,4-addition of alkyl magnesium chlorides to a,/ -disubstituted (/ )-enesultams 60. Subsequent protonation of the reaction product gives compound 61c as the major product (Scheme 2-30 and Table 2-11).56... 

We can now begin to see some of the implications of the theory and in which directions its applicability can be tested. In the course of these considerations one must always keep in mind that the rate of the ionogenic reaction (iii) ( left to right rate-constant k() is very small in comparison with the rates of polymerisation and of complex formation (reaction (ii)) and that the equilibrium concentration of ions is very small (see Table 1). 

Few relevant data are available. Both equilibrium and rate constants have been measured for very few reaction series in solution, but comparisons are possible for lactone and thiolactone formation, and for a few anhydrideforming reactions (Tables 4 and 5). For lactone formation (Table 4) the EM for the rate process is of the same order of magnitude as that derived from the equilibrium constant data, and in some cases actually exceeds it (though only in one case by an amount clearly greater than the estimated uncertainty which is nominally a factor of 4 for these ratios). Lactonization generally involves rate-limiting breakdown of the tetrahedral intermediate, and the transition state is expected to be late and thus close in structure to the conjugate acid of the lactone. 

It is worth mentioning at this point that according to Normant et al. (1975) simple polyamines such as tetramethylethylenediamine (TMEDA) are even more active than [2.2.2]-cryptand in the benzylation of acetates in acetonitrile under liquid-solid conditions. These authors suggested that the activity was due to salt solubilization by cation complexation and not to formation of a quaternary ammonium ion since the latter showed no activity. This statement, however, is not in line with the results of Cote and Bauer (1977), who were unable to detect any interaction between K+ and TMEDA in acetonitrile. Furthermore, Vander Zwan and Hartner (1978) found Aliquat 336 (tricaprylylmethylammonium chloride) to be almost as effective as TMEDA in this reaction (Table 30). It might well be, however, that in amine-catalysed benzylation reactions the quaternary salt formed in situ acts both as a reactant and as a phase-transfer catalyst, since Dou et al. (1977) have shown that the benzyltriethylammonium ion is a powerful benzylation agent. 

To what extent is the macroscopic proton release the direct expression of the metal/surface site reactions Table V compares the macroscopic proton coefficients (Xp ) ) with the coefficient expected if only the Cd(II) surface reactions are considered is the proton coefficient determined by considering the mole fraction of Cd(II) surface species and their formation reactions (Figure 14b). For example, when pSOH is 2.84, y = 0.11 x 1 + 0.89 x 2 = 1.89. At high alumina concentrations pSOH 2.14-2.53) the single surface reaction required to fit the data sets a limiting proton release of 2.0. 

The dynamic features of each of the thiols were subsequently evaluated in transthiolesterification reactions in buffered D O solution (NaOD/D PO, pD 7.0) with the ACh analog acetylthiocholine [ASCh (14), Table 6.1]. Formation/thiolysis of each thiolester was carefully followed by H-NMR spectroscopy at different time intervals, and exchange rate and equilibrium composition were determined for each combination. The rate of exchange was directly correlated to the p/f of the thiols the lower the pK, the faster the exchange reaction (Table 6.1). Thiols having pK values lower than 8.5 reached equilibrium very rapidly. The results also showed that the majority of thiols produce equilibrium concentrations that are close to... 

Table 7 Kinetic parameters for formation reactions from aquapentacyanoferrate(II), [Fe(CN)5(H20)] +L,...

Kinetics and mechanisms of complex formation have been reviewed, with particular attention to the inherent Fe +aq + L vs. FeOH +aq + HL proton ambiguity. Table 11 contains a selection of rate constants and activation volumes for complex formation reactions from Fe " "aq and from FeOH +aq, illustrating the mechanistic difference between 4 for the former and 4 for the latter. Further kinetic details and discussion may be obtained from earlier publications and from those on reaction with azide, with cysteine, " with octane-and nonane-2,4-diones, with 2-acetylcyclopentanone, with fulvic acid, and with acethydroxamate and with desferrioxamine. For the last two systems the various component forward and reverse reactions were studied, with values given for k and K A/7 and A5, A/7° and A5 ° AF and AF°. Activation volumes are reported and consequences of the proton ambiguity discussed in relation to the reaction with azide. For the reactions of FeOH " aq with the salicylate and oxalate complexes d5-[Co(en)2(NH3)(sal)] ", [Co(tetraen)(sal)] " (tetraen = tetraethylenepentamine), and [Co(NH3)5(C204H)] both formation and dissociation are retarded in anionic micelles. 

The protodelithiation enthalpy of n-propyl lithium is very nearly the same as for the n-butyl species, —219 2 kJmoP. From reaction 10 with w-butyl lithium as the benchmark species and the enthalpies of formation of the hydrocarbons in their gaseous reference states, the enthalpy of formation of n-propyl lithium is calculated as ca —91 klmoP, a value consistent with that of —86 kJ moP derived from w-PrMgBr in an earlier section. If the reference state of n-butane is taken as the liquid instead, the enthalpy of formation of n-propyl lithium is ca —70 kJ moP, a value consistent with another previous derivation of ca —73 kJmoP. At least with respect to consistency with the enthalpies of formation in Table 1, the best reference state for ethane and propene is the gas it is not yet clear which is better for butane. 

Figure 16.3 (Before correction) An example of a table with common formatting errors. Table 1. Yield of 3 in the reaction of la and 2a.s...

Table 6.2 Ruthenium catalyzed indene formation reaction. ...

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