How Fast Do R?X Bonds Ionize? A Semiquantitative Approach

The correlation equation log k(25 degrees C) = sf(Nf + Ef), where sf and Nf are nucleofuge-specific parameters referring to leaving group/solvent combinations and Ef are electrofuge-specific parameters referring to the incipient carbocation R+, are used to predict ionization rate constants of alkyl derivatives R--X. We show how to employ the Ef parameters of reference electrofuges and the sf and Nf parameters of reference nucleofuges reported in the preceding article for determining further sf, Nf, and Ef parameters. Since sf is usually close to 1.0, one comes to the semiquantitative rule that at 25 degrees C, compounds R--X for which Nf + Ef>-2 will solvolyze with half-lives of less than a minute, while the solvolysis half-lives will exceed 1 month if Nf + Ef<-6.5.     

Kinetics of the solvolyses of benzhydryl derivatives: basis for the construction of a comprehensive nucleofugality scale

A series of 21 benzhydrylium ions (diarylmethylium ions) are proposed as reference electrofuges for the development of a general nucleofugality scale, where nucleofugality refers to a combination of leaving group and solvent. A total of 167 solvolysis rate constants of benzhydrylium tosylates, bromides, chlorides, trifluoroacetates, 3,5-dinitrobenzoates, and 4-nitrobenzoates, two-thirds of which have been determined during this work, were subjected to a least-squares fit according to the correlation equation log k(25 degrees C) = sf(Nf + Ef), where sf and Nf are nucleofuge-specific parameters and Ef is an electrofuge-specific parameter. Although nucleofuges and electrofuges characterized in this way cover more than 12 orders of magnitude, a single set of the parameters, namely sf, Nf, and Ef, is sufficient to calculate the solvolysis rate constants at 25 degrees C with an accuracy of +/-16 %. Because sf approximately 1 for all nucleofuges, that is, leaving group/solvent combinations, studied so far, qualitative discussions of nucleofugality can be based on Nf.     

Nucleofugality of phenyl and methyl carbonates

A series of X,Y-substituted benzhydryl phenyl carbonates 1 and X,Y-substituted benzhydryl methyl carbonates 2 were subjected to solvolysis in different methanol/water, ethanol/water, and acetone/water mixtures at 25 degrees C. The LFER equation, log k = sf(Ef + Nf), was used to derive the nucleofuge-specific parameters (Nf and sf) for phenyl carbonate (1LG) and methyl carbonate (2LG) leaving groups in a given solvent in SN1 type reaction. Kinetic measurements showed that phenyl carbonates solvolyze one order of magnitude faster than methyl carbonates. Optimized geometries of 1LG and 2LG at B3LYP/6-311G(d,p), B3LYP/6-311++G(d,p), and MP2(full)/6-311++G(d,p) levels revealed that negative charge delocalization in carbonate anions to all three oxygen atoms occurs due to negative hyperconjugation. Phenyl carbonate (1LG) is a better leaving group (Nf = -0.84 +/- 0.07 in 80% v/v aq EtOH) than methyl carbonate 2LG (Nf = -1.84 +/- 0.07 in 80% v/v aq EtOH) because of more pronounced negative hyperconjugation, which is characterized with a more elongated RO-C bond and more increased RO-C-CO angle in 1LG than in 2LG. Calculated affinities of benzhydryl cation toward methyl and phenyl carbonate anions (DeltaDeltaEaff = 11.7 kcal/mol at the B3LYP/6-311++G(d,p) level and DeltaDeltaEaff = 2.7 kcal/mol at the PCM-B3LYP/6-311++G(d,p) level in methanol, respectively) showed that 1LG is more stabilized than 2LG, which is in accordance with greater solvolytic reactivity of 1 than 2.     

DFT-PCM studies of solvent effects on the cross-interaction constants in benzhydryl cation and anion formation

The Hammett rho+ and rho- values have been determined by varying substituent Y' for a given Y in the benzhydryl cation and anion formation (YH4C6-CH-C6H4Y' where C is a cationic or an anionic center) at the RHF/3-21G, RHF/6-31G, RHF/6-31+G, and B3LYP/6-31+G levels. The failure of RHF theory in accounting for the stabilization by delocalization leads to the smaller magnitudes of rho+ and rho- with electron-donating and -withdrawing substituents, Y, respectively, than the corresponding DFT values. The effects of solvent (benzene, dichloroethane, and acetonitrile) on the rho values were calculated by applying the conductor polarizable continuum model method to the DFT results. Finally, the cross-interaction constants (rho(YY)') and their variation with solvent were determined. As the polarity (dielectric constant, epsilon) of the solvent is increased, the magnitude of rho+ and rho- decreased, whereas that of rho(YY)' increased. Satisfactory correlations were obtained between rho values (rho+, rho- and rho(YY)') and the Kirkwood function f(k) (= epsilon - 1/2epsilon + 1). The rho(YY)' values are negative with a magnitude greater for the anionic (rho(YY)'-) than the cationic (rho(YY)'+) system.     

Nucleofugality and nucleophilicity of fluoride in protic solvents

A series of p-substituted benzhydryl fluorides (diarylfluoromethanes) were prepared and subjected to solvolysis reactions, which were followed conductometrically. The observed first-order rate constants k(1)(25 °C) were found to follow the correlation equation log k(1)(25 °C) = s(f)(N(f) + E(f)), which allowed us to determine the nucleofuge-specific parameters N(f) and s(f) for fluoride in different aqueous and alcoholic solvents. The rates of the reverse reactions were measured by generating benzhydrylium ions (diarylcarbenium ions) laser flash photolytically in various alcoholic and aqueous solvents in the presence of fluoride ions and monitoring the rate of consumption of the benzhydrylium ions by UV-vis spectroscopy. The resulting second-order rate constants k(-1)(20 °C) were substituted into the correlation equation log k(-1) = s(N)(N + E) to derive the nucleophilicity parameters N and s(N) for fluoride in various protic solvents. Complete Gibbs energy profiles for the solvolysis reactions of benzhydryl fluorides are constructed.     

Kinetic substituent and solvent effects in 1,3-dipolar cycloaddition of diphenyldiazomethanes with fullerenes C60 and C70: a comparison with the addition to TCNE, DDQ, and chloranil

Kinetics of 1,3-dipolar cycloaddition of a series of meta- and para-substituted diphenyldiazomethanes (DDMs) with fullerenes C60 and C70 as dipolarophiles have been investigated in toluene at 30 degrees C. Fullerene C60 was ca. 1.5 times more reactive than C70. The rate constants (k) for the primary [3 + 2] additions increased with the increase of the electron-releasing ability of the meta and para substituent. The log k/k0 values were well correlated by the Yukawa-Tsuno (Y-T) equations with the smaller negative rho values (-1.6 and -1.7 for C60 and C70) and the reduced resonance reaction constants r (0.22 and 0.17) compared to similar reactions of common acceptors, TCNE, DDQ, and chloranil (CA). The plots of log k (acceptor) versus log k (C60) as reference gave good regression equations and the slopes became larger in the order of TCNE > DDQ > CA > C70 > or = C60. The rates were also found to decrease with the increase of solvent polarity due to the ground-state solvation of fullerenes. However, the relative reactivity of these acceptors toward the unsubstituted DDM increased in the order of DDQ > C60 > or = C70 > TCNE > CA. The unexpected higher reactivity of fullerenes was interpreted in terms of the inherent steric strain by the pyramidalization of the sp2 C-atoms as well as the shorter [6,6] bonds with larger pi-electron densities.     

Application of the NT solvent nucleophilicity scale to attack at phosphorus: solvolyses of N,N,N',N'-tetramethyldiamidophosphorochloridate

The specific rates of solvolysis of N,N,N',N'-tetramethyldiamidophosphorochloridate have been measured at 25.0 degrees C in 31 solvents. Analysis with the extended Grunwald-Winstein equation leads to sensitivities toward changes in solvent nucleophilicity (l) of 1.20 +/- 0.07 and toward changes in solvent ionizing power (m) of 0.69 +/- 0.04. The correlation is improved by omission of the four data points for 2,2,2-trifluoroethanol-ethanol mixtures (F-test value from 155 to 320) with very small reductions in both l and m values. Activation parameters are reported for eight of the solvolyses. The l and m values are very similar to those previously reported for solvolyses of several arenesulfonyl chlorides, consistent with a concerted substitution process. This assignment is supported by a large k(Cl)/k(F) ratio for hydrolysis and a corresponding ratio for hydroxide-assisted hydrolysis of 178. The stereochemistry of nucleophilic attack at tetracoordinate phosphorus(V) is discussed.     

S(N)2 Mechanism for Alcoholysis, Aminolysis, and Hydrolysis of Acetyl Chloride

First-order solvolysis rate constants are reported for solvolyses of acetyl chloride in methanol and MeOD, and in binary aqueous mixtures with acetone, acetonitrile, ethanol, methanol, and trifluoroethanol at 0 degrees C. Product selectivities (S = [MeCOOR]/[MeCOOH] x [water]/[alcohol]) are reported for solvolyses in ethanol/ and methanol/water at 0 degrees C. Solvolyses of acetyl chloride show a high sensitivity to changes in solvent ionizing power, consistent with C-Cl bond cleavage. As the solvent is varied from pure ethanol (or methanol) to water, S values and rate-rate profiles show no evidence for the change in reaction channel observed for solvolyses of benzoyl and trimethylacetyl chlorides. However, using rate ratios in 40% ethanol/water and 97% trifluoroethanol/water (solvents of similar ionizing power but different nucleophilicities) to compare sensitivities to nucleophilic attack, solvolyses of acetyl chloride are over 20-fold more sensitive to nucleophilic attack than benzoyl chloride. The solvent isotope effect of 1.29 (MeOH/MeOD) for acetyl chloride is similar to that for p-methoxybenzoyl chloride (1.22) and is lower than for benzoyl chloride (1.55). Second-order rate constants for aminolyses of acetyl chloride with m-nitroaniline in methanol at 0 degrees C show that acetyl chloride behaves similarly to p-methoxybenzoyl chloride, whereas benzoyl chloride is 40-fold more sensitive to the added amine. The results indicate mechanistic differences between solvolyses of acetyl and benzoyl chlorides, and an S(N)2 mechanism is proposed for solvolyses and aminolyses by m-nitroaniline of acetyl chloride (i.e. these reactions are probably not carbonyl additions, but a strong sensitivity to nucleophilic attack accounts for their high rates).     

Solvent polarity and organic reactivity in mixed solvents: evidence using a reactive molecular probe to assess the role of preferential solvation in aqueous alcohols

Product selectivities [S = ([ester product]/[acid product]) x ([water]/[alcohol solvent])] are reported for solvolyses of p-methoxybenzoyl chloride (2) in aqueous methanol, ethanol, 2,2,2-trifluoroethanol, n-propyl alcohol, isopropyl alcohol, and tert-butyl alcohol at 25, 35, and 45 degrees C. S values are small and depend significantly on the alcohol cosolvent, varying from 1.3 in methanol to 0.1 in tert-butyl alcohol, but S depends only slightly on the solvent composition, and on the temperature. As S adjusts the product ratios for changes in bulk solvent compositions, it is suggested that preferential solvation by either alcohol or water at the reaction site is not a major factor influencing rates or products. Logarithms of rates of solvolyses of 2 correlate well with Kosower Z values (based on solvatochromism). In contrast, another solvatochromic polarity index, E(T)(30), shows "dispersion" in correlations with the solvent ionizing power parameter, Y(OTs), probably due to aromatic ring and other solvation effects.     

Solvent sensitivity of ortho substituent effect on 13C NMR chemical shift of the carboxyl carbon (δco) in benzoic acid

A reverse ortho effect is observed for the (13)C NMR chemical shifts of the carboxyl carbon (δ(co)) in benzoic acids measured in aprotic solvents of varying polarity. The ortho effect on δ(co) is best described by a combination of the reverse field and steric accelerating effects of the substituent in an 80: 20 pattern in apolar aprotic solvents and a 60: 40 pattern in dipolar aprotic ones. Interestingly, no good enough correlation was found between δ(co) and log k(1) of the acids measured in similar solvents. A critical analysis of the results clearly indicates the use of an apolar aprotic solvent and not a dipolar aprotic one as the solvent of choice for investigating intrinsic substituent effects on δ(c) in an aromatic system.     

Mechanisms of solvolyses of acid chlorides and chloroformates. Chloroacetyl and phenylacetyl chloride as similarity models

[reaction: see text] Rate constants and product selectivities (S = ([ester product]/[acid product]) x ([water]/[alcohol solvent]) are reported for solvolyses of chloroacetyl chloride (3) at -10 degrees C and phenylacetyl chloride (4) at 0 degrees C in ethanol/ and methanol/water mixtures. Additional kinetic data are reported for solvolyses in acetone/water, 2,2,2-trifluoroethanol(TFE)/water, and TFE/ethanol mixtures. Selectivities and solvent effects for 3, including the kinetic solvent isotope effect (KSIE) of 2.18 for methanol, are similar to those for solvolyses of p-nitrobenzoyl chloride (1, Z = NO(2)); rate constants in acetone/water are consistent with a third-order mechanism, and rates and products in ethanol/ and methanol/water mixtures can be explained quantitatively by competing third-order mechanisms in which one molecule of solvent (alcohol or water) acts as a nucleophile and another acts as a general base (an addition/elimination reaction channel). Selectivities increase for 3 as water is added to alcohol. Solvent effects on rate constants for solvolyses of 3 are very similar to those of methyl chloroformate, but acetyl chloride shows a lower KSIE, and a higher sensitivity to solvent-ionizing power, explained by a change to an S(N)2/S(N)1 (ionization) reaction channel. Solvolyses of 4 undergo a change from the addition/elimination channel in ethanol to the ionization channel in aqueous ethanol (<80% v/v alcohol). The reasons for change in reaction channels are discussed in terms of the gas-phase stabilities of acylium ions, calculated using Gaussian 03 (HF/6-31G(d), B3LYP/6-31G(d), and B3LYP/6-311G(d,p) MO theory).     

Catalysis of the ethanolysis of aryl methyl phenyl phosphinate esters by alkali metal ions: transition state structures for uncatalyzed and metal ion-catalyzed reactions

This paper reports on a spectrophotometric kinetic study of the effects of the alkali metal ions Li+ and K+ on the ethanolysis of the aryl methyl phenyl phosphinate esters 3a-f in anhydrous ethanol at 25 degrees C. Rate data obtained in the absence and presence of complexing agents afford the second-order rate constants for the reaction of free ethoxide (k(EtO-)) and metal ion-ethoxide ion pairs (k(MOEt)). The sequence k(EtO-) < k(MOEt) is established for all the substrates, contrary to the generally observed reactivity order in nucleophilic substitution processes. The quantities deltaG(ip), deltaG(ts) and DeltaG(cat), which quantify the observed alkali metal ion effect in terms of transition state stabilization through chelation of the metal ion, give the order deltaG(ts) > deltaG(ip) for Li+ and K+. Hammett plots show significantly better correlation of rates with sigma and sigma(o) substituent constants than with sigma-, yielding moderately large rho(rho(o)) values that are consistent with a stepwise mechanism in which formation of a pentacoordinate (phosphorane) intermediate is the rate-limiting step. The range of the values of the selectivity parameter, rho(n) (= rho]/rho(eq)), 1.3-1.6, obtained for the uncatalyzed and alkali metal ion catalyzed reactions indicates that there is no significant perturbation of the transition state (TS) structure upon chelation of the metal ions. This finding is relevant to the mechanism of enzymatic phosphoryl transfer involving metal ion co-factors. The present results enable one to compare structural effects for nucleophilic reactions of several series of organophosphorus substrates. It is shown that the order of reactivity of the substrates: 4-nitrophenyl dimethyl phosphinate (2) > 3a > 4-nitrophenyl diphenyl phosphinate (1) is determined mainly by the steric effects of the alkyl/aryl substituents around the central P atom in the TS of the reaction.     

Effect of phenyl substituent on the dimerization of copper(II)-carboxylate in solvent extraction of copper(II) with phenylacetic acid

The effects of the phenyl substituent on the dimerization of copper(II) carboxylate in the solvent extraction of copper(II) with phenylacetic acid using benzene and 1-octanol as a solvent were investigated, at 25 degrees and at the aqueous ionic strength of 0.1M (NaClO(4)). The dimerization of copper(II) phenylacetate has been found to be written as: 2CuA(2)Cu(2)A(4) in 1-octanol, and 2CuA(2)(HA)(2)Cu(2)A(4)(HA)(2) + (HA)(2) in benzene, with the dimerization constants, log K = 2.24 and log K = 4.19, respectively. It was proved that the phenyl group inhibits the formation of the dimeric copper(II) phenylacetate, and its effect is partially shielded by a methylene substituent.     

Structural effects on the solvolytic reactivity of carboxylic and sulfonic acid chlorides. Comparisons with gas-phase data for cation formation

Kinetic data for solvolyses of 28 acid chlorides in 97% w/w trifluoroethanol (TFE)-water spanning over 10 (9) in rate constant at 25 degrees C are obtained directly or by short extrapolation from published values. G3 calculations of the energy required for cation formation in the gas phase are validated from proton affinities and from other experimental data. G3 calculations of heterolytic bond dissociation enthalpies (HBDEs) for formation of cations from acid chlorides in the gas phase show the following trends when compared with the solvolysis rate constants: (i) electron-rich sulfonyl chlorides and most carboxylic acid chlorides, including thione derivatives, give a satisfactory linear correlation with a significant negative slope; (ii) most sulfonyl chlorides and some chloroformates and thio derivatives have higher HBDEs and fit another correlation with a small, negative slope. A significant deviation is observed for the acyl series (RCOCl), for which both solvolysis rates and HBDEs increase in the order R = Bu ( t ) < Pr ( i ) < Et < Me. The deviation may be explained either by a prior hydration mechanism or preferably by electrostatic effects on the formation of small cations. The above results of structural effects support independent evidence from solvent effects that cationic ionization reaction pathways (with nucleophilic solvent assistance or S N2 character) are involved in the solvolyses of acid chlorides.     

Kinetics of the reactions of halide anions with carbocations: quantitative energy profiles for s(n)1 reactions

Rate constants for the reactions of Laser flash photolytically generated benzhydrylium ions (diarylcarbenium ions) with halide ions have been determined in various solvents, including neat and aqueous acetonitrile as well as some alcohols. Substitution of the rate constants into the correlation equation log k = s(N + E) yields the nucleophilicity parameters N for the halide ions in different solvents. Linear correlations with negative slopes are found between the nucleophilicity parameters N for Cl(-) and Br(-) in different solvents and the solvent ionizing powers Y of the corresponding solvents. Increasing halide solvation reduces the rates of carbocation/chloride combinations by approximately half as much as it increases the rates of ionizations of benzhydryl chlorides. Comparison of the solvent dependent nucleophilicity parameters N of halide anions and the nucleophilicity parameters N(1) for solvents yields a quantitative prediction of common ion rate depression, as demonstrated by the analysis of a variety of literature reported mass-law constants alpha. Combination of the rate constants for the reactions of benzhydrylium ions with halide ions (k(-)()(1)) reported in this work with the ionization constants of benzhydryl halides (k(1)) and the recently reported rate constants for the reactions of benzhydrylium ions with solvents (k(2)) yields complete quantitative free energy profiles for solvolysis reactions. The applicability of Hammond's postulate for interpreting solvolysis reactions can thus be examined quantitatively.     

Solvent nucleophilicity

The rates of the reactions of benzhydrylium ions (diarylcarbenium ions) with solvent mixtures of variable composition (water/acetonitrile, methanol/acetonitrile, ethanol/acetonitrile, ethanol/water, and trifluoroethanol/water) have been determined photometrically by conventional UV-vis spectroscopy, stopped-flow methods, and laser flash techniques. It has been shown that the first-order rate constants follow the previously published relationship log k(20 degrees C) = s(N + E), where E is an empirical electrophilicity parameter, N is an empirical nucleophilicity parameter, and s is a nucleophile-specific slope parameter. From plots of log k versus E of the benzhydrylium ions are derived the solvent nucleophilicity parameters s and N, the latter of which are designated as N1 to emphasize that their use in the quoted correlation equation gives rise to first-order rate constants. A linear correlation between N1 and Kevill's solvent nucleophilicity NT based on S-methyldibenzothiophenium ions is reported, which allows one to interconvert the two sets of data. Because the N1 values are directly comparable to the previously reported nucleophilicity parameters N for pi-systems (www.cup.uni-muenchen.de/oc/mayr/), the systematic design of Friedel-Crafts reactions with solvolytically generated carbocations becomes possible.     

Ruthenium‐Catalyzed Asymmetric Hydrogenation of 3‐Oxoglutaric Acid Derivatives: A Study of Unconventional Solvent and Substituent Effects

A series of 3‐oxoglutaric acid derivatives have been hydrogenated in different solvents in the presence of [RuCl(benzene)(S)‐SunPhos]Cl (SunPhos=(2,2,2′,2′‐tetramethyl‐[4,4′‐bibenzo[d][1,3]dioxole]‐5,5′‐diyl)bis(diphenylphosphine)). Unlike simple β‐keto acid derivatives, these advanced analogues can be readily hydrogenated in uncommon solvents such as THF, CH₂Cl₂, acetone, and dioxane with high enantioselectivities. Two possible catalytic cycles have been proposed to explain the different reactivities of these 1,3,5‐tricarbonyl substrates in the tested solvents. The C‐2 and C‐4 substituents had notable but irregular influence on the reactivity and enantioselectivity of the reactions. More pronounced solvent effects were observed: the ee values increased from around 20 % in EtOH or THF to 90 % in acetone. Inversion of the product configuration was observed when the solvent was changed from EtOH to THF or acetone, and a mixed solvent system can lead to better enantioselectivity than a single solvent.     

How Nucleophilic Are Diazo Compounds?

The kinetics of the reactions of benzhydryl cations with eight diazo compounds 1 a-g were investigated photometrically in dichloromethane. The nucleophilicity parameters N and slope parameters s of these diazo compounds were derived from the equation log k (20 degrees C)=s (E+N) and compared with the nucleophilicities of other pi systems (alkenes, arenes, silyl enol ethers, silyl ketene acetals). It is shown that the nucleophilic reactivities of diazo compounds cover more than ten orders of magnitude, being comparable to that of styrene on the low reactivity end and to that of enamines on the high reactivity end. The rate-determining step of these reactions is the electrophilic attack at the diazo-carbon atom to yield diazonium ions, which rapidly lose nitrogen.     

Photogeneration of Benzhydryl Cations by Near-UV Laser Flash Photolysis of Pyridinium Salts

Laser flash irradiation of substituted N-benzhydryl pyridinium salts yields benzhydryl cations (diarylcarbenium ions) and/or benzhydryl radicals (diarylmethyl radicals). The use of 3,4,5-triamino-substituted pyridines as photoleaving groups allowed us to employ the third harmonic of a Nd/YAG laser (355 nm) for the photogeneration of benzhydryl cations. In this way, benzhydryl cations can also be photogenerated in the presence of aromatic compounds and in solvents which are opaque at the wavelength of the quadrupled Nd/YAG laser (266 nm). To demonstrate the scope and limitations of this method, the rate constants for the bimolecular reactions of benzhydryl cations with several substituted pyridines were determined in acetonitrile and with water in acetone. The obtained data agree with results obtained by stopped-flow UV-vis spectroscopic measurements. The rate constants for the reaction of the 4,4'-bis[methyl(2,2,2-trifluoroethyl)amino]benzhydrylium ion with 4-(dimethylamino)pyridine were also determined in dimethyl sulfoxide, N,N-dimethylformamide, and acetone. From the second-order rate constants, we derived the nucleophilicity parameters N and s(N) for the substituted pyridines, as defined by the linear free energy relationship, log k(2) = s(N)(N + E).     

Quenching of singlet molecular oxygen (1O2) by azide anion in solvent mixtures.

The azide ion is a strong physical quencher of singlet molecular oxygen (1O2) and is frequently employed to show involvement of 1O2 in oxidation processes. Rate constants (k(q)) for the quenching of 1O2 by azide are routinely used as standards to calculate k(q) values for quenching by other substrates. We have measured k(q) for azide in solvent mixtures containing deuterium oxide (D2O), acetonitrile (MeCN), 1,4-dioxane, ethanol (EtOH), propylene carbonate (PC), or ethylene carbonate (EC), mixtures commonly used for many experimental studies. The rate constants were calculated directly from 1O2 phosphorescence lifetimes observed after laser pulse excitation of rose bengal (RB), used to generate 1O2. In aqueous mixtures with MeCN and carbonates, the rate constant increased nonlinearly with increasing volume of organic solvent in the mixtures. k(q) was 4.78 x 10(8) M(-1) s(-1) in D2O and increased to 26.7 x 10(8) and 27.7 x 10(8) M(-1) s(-1) in 96% MeCN and 97.7% EC/PC, respectively. However, in EtOH/D2O mixtures, k(q) decreased with increasing alcohol concentration. This shows that a higher solvent polarity increases the quenching efficiency, which is unexpectedly decreased by the proticity of aqueous and alcohol solvent mixtures. The rate constant values increased with increasing temperature, yielding a quenching activation energy of 11.3 kJ mol(-1) in D2O. Our results show that rate constants in most solvent mixtures cannot be derived reliably from k(q) values measured in pure solvents by using a simple additivity rule. We have measured the rate constants with high accuracy, and they may serve as a reliable reference to calculate unknown k(q) values.