Scandium ion-promoted reduction of heterocyclic N=N double bond. Hydride transfer vs electron transfer

Hydride transfer from 10-methyl-9,10-dihydroacridine (AcrH(2)) to 3,6-diphenyl-1,2,4,5-tetrazine (Ph(2)Tz), which contains a N=N double bond, occurs efficiently in the presence of Sc(OTf)(3) (OTf = OSO(2)CF(3)) in deaerated acetonitrile (MeCN) at 298 K, whereas no reaction occurs in the absence of Sc(3+). The observed second-order rate constant (k(obs)) increases with increasing Sc(3+) concentration to approach a limited value. When AcrH(2) is replaced by the dideuterated compound (AcrD(2)), the rate of Sc(3+)-promoted hydride transfer exhibits the same primary kinetic isotope effect (k(H)/k(D) = 5.2+/-0.2), irrespective of Sc(3+) concentration. Scandium ion also promotes an electron transfer from CoTPP (TPP(2)(-) = tetraphenylporphyrin dianion) and 10,10'-dimethyl-9,9'-biacridine [(AcrH)(2)] to Ph(2)Tz, whereas no electron transfer from CoTPP or (AcrH)(2) to Ph(2)Tz occurs in the absence of Sc(3+). In each case, the observed second-order rate constant of electron transfer (k(et)) shows a first-order dependence on [Sc(3+)] at low concentrations and a second-order dependence at higher concentrations. Such dependence of k(et) on [Sc(3+)] is ascribed to formation of 1:1 and 1:2 complexes between Ph(2)Tz(*)(-) and Sc(3+) at the low and high concentrations of Sc(3+), respectively, which results in acceleration of the rate of electron transfer. The formation of 1:2 complex has been confirmed by the ESR spectrum in which the hyperfine structure is different from that of free Ph(2)Tz(*)(-). The 1:2 complex formation results in the saturated kinetic dependence of k(obs) on [Sc(3+)] for the Sc(3+)-promoted hydride transfer, which proceeds via Sc(3+)-promoted electron transfer from AcrH(2) to Ph(2)Tz, followed by proton transfer from AcrH(2)(*)(+) to the 1:1 Ph(2)Tz(*)(-)-Sc(3+) complex and the subsequent facile electron transfer from AcrH(*) to Ph(2)TzH(*). The effects of counteranions on the Sc(3+)-promoted electron transfer and hydride transfer reactions are also reported.     

Scandium ion-promoted photoinduced electron transfer from electron donors to acridine and pyrene. Essential role of scandium ion in photocatalytic oxygenation of hexamethylbenzene

Photoinduced electron transfer from a variety of electron donors including alkylbenzenes to the singlet excited state of acridine and pyrene is accelerated significantly by the presence of scandium triflate [Sc(OTf)(3)] in acetonitrile, whereas no photoinduced electron transfer from alkylbenzenes to the singlet excited state of acridine or pyrene takes place in the absence of Sc(OTf)(3). The rate constants of the Sc(OTf)(3)-promoted photoinduced electron-transfer reactions (k(et)) of acridine to afford the complex between acridine radical anion and Sc(OTf)(3) remain constant under the conditions such that all the acridine molecules form the complex with Sc(OTf)(3). In contrast to the case of acridine, the k(et) value of the Sc(OTf)(3)-promoted photoinduced electron transfer of pyrene increases with an increase in concentration of Sc(OTf)(3) to exhibit first-order dependence on [Sc(OTf)(3)] at low concentrations, changing to second-order dependence at high concentrations. The first-order and second-order dependence of k(et) on [Sc(OTf)(3)] is ascribed to the 1:1 and 1:2 complexes formation between pyrene radical anion and Sc(OTf)(3). The positive shifts of the one-electron redox potentials for the couple between the singlet excited state and the ground-state radical anion of acridine and pyrene in the presence of Sc(OTf)(3) as compared to those in the absence of Sc(OTf)(3) have been determined by adapting the free energy relationship for the photoinduced electron-transfer reactions. The Sc(OTf)(3)-promoted photoinduced electron transfer from hexamethylbenzene to the singlet excited state of acridine or pyrene leads to efficient oxygenation of hexamethylbenzene to produce pentamethylbenzyl alcohol which is further oxygenated under prolonged photoirradiation of an O(2)-saturated acetonitrile solution of hexamethylbenzene in the presence of acridine or pyrene which acts as a photocatalyst together with Sc(OTf)(3). The photocatalytic oxygenation mechanism has been proposed based on the studies on the quantum yields, the fluorescence quenching, and direct detection of the reaction intermediates by ESR and laser flash photolysis.     

Metal ion-promoted intramolecular electron transfer in a ferrocene-naphthoquinone linked dyad. Continuous change in driving force and reorganization energy with metal ion concentration

Thermal intramolecular electron transfer from the ferrocene (Fc) to naphthoquinone (NQ) moiety occurs efficiently by the addition of metal triflates (M(n)()(+): Sc(OTf)(3), Y(OTf)(3), Eu(OTf)(3)) to an acetonitrile solution of a ferrocene-naphthoquinone (Fc-NQ) linked dyad with a flexible methylene and an amide spacer, although no electron transfer takes place in the absence of M(n)()(+). The resulting semiquinone radical anion (NQ(*)(-)) is stabilized by the strong binding of M(n)()(+) with one carbonyl oxygen of NQ(*)(-)( )()as well as hydrogen bonding between the amide proton and the other carbonyl oxygen of NQ(*)(-). The high stability of the Fc(+)()-NQ(*)(-)/M(n)()(+)() complex allows us to determine the driving force of electron transfer by the conventional electrochemical method. The one-electron reduction potential of the NQ moiety of Fc-NQ is shifted to a positive direction with increasing concentration of M(n)()(+), obeying the Nernst equation, whereas the one-electron oxidation potential of the Fc moiety remains the same. The driving force dependence of the observed rate constant (k(ET)) of M(n)()(+)-promoted intramolecular electron transfer is well evaluated in light of the Marcus theory of electron transfer. The driving force of electron transfer increases with increasing concentration of M(n)()(+) [M(n)()(+)], whereas the reorganization energy of electron transfer decreases with increasing [M(n)()(+)] from a large value which results from the strong binding between NQ(*)(-) and M(n)()(+).     

Europium ion catalyzed methanolysis of esters at neutral pH and ambient temperature. catalytic Involvement of Eu3+(CH3O-)(CH3OH)x

The Eu(3+)-promoted methanolysis of three esters, p-nitrophenyl acetate (1), phenyl acetate (2), and ethyl acetate (3) is reported, as well as the potentiometric titration of Eu(3+) in MeOH at various [Eu(SO(3)CF(3))(3)] (SO(3)CF(3) = OTf). The titration data are analyzed in terms of two ionizations corresponding to macroscopic and values, which are respectively defined as the values at which the [CH(3)O(-)]/[Eu(3+)] = 0.5 and 1.5. As a function of increasing [Eu(OTf)(3)], increases slightly due to a proposed Eu(3+)/(-)OTf ion pairing effect, which tends to reduce the acidity of the metal-coordinated CH(3)OH, while decreases due to the formation of Eu(3+) dimers and oligomers which stabilize the (Eu(3+)(CH(3)O(-))(2))(n)forms through bridging of the methoxides between two or more metal ions. For ester 1, a detailed kinetic analysis of the reaction rates as a function of both [Eu(OTf)(3)] and in buffered methanol reveals that the /second-order rate constant (k(2)) plot for the catalyzed reaction follows a bell-shaped profile, suggesting that the active form is a Eu(3+)(CH(3)O(-)) monomer with a kinetic of 6.33 +/- 0.06 for formation and a of 8.02 +/- 0.10 for its conversion into the inactive (Eu(3+)(CH(3)O(-))(2))(n)oligomeric form. At higher values, plots of k(obs) vs [Eu(OTf)(3)] are linear at low metal concentration and plateau at higher metal concentration due to the formation of inactive higher order aggregates. The Eu(3+)(CH(3)O(-)) catalysis of the methanolysis of esters 1, 2, and 3 is substantial. Solutions of 10(-2) M of the catalyst at 7.12 accelerate the reaction relative to the methoxide reaction at that by 8 530 000-, 195 000 000- and 7 813 000-fold, respectively.     

Billion-fold acceleration of the methanolysis of paraoxon promoted by La(OTf)3 in methanol

The methanolysis of the insecticide paraoxon (2) was investigated in methanol solution containing varying [La(OTf)(3)] (OTf = (-)OS(O)(2)CF(3)) as a function of at 25 degrees C. Plots of the pseudo-first-order rate constants (k(obs)) for methanolysis as a function of [La(OTf)(3)](total) were obtained under buffered conditions from 5.15 to 10.97, and the slopes of the linear parts of these were used to determine the second-order rate constants (k(2)(obs)) for the La(3+)-catalyzed methanolysis of 2. Detailed analysis of the potentiometric titration data of La(OTf)(3) in methanol through fits to a multicomponent equilibrium mixture of dimers of general stoichiometry La(3+)(2)((-)OCH3)n, where n assumes values of 1-5, gives the equilibrium distribution of each as a function of. These data, when fit to a second expression describing k(2)(obs) in terms of a linear combination of individual rate constants k(2)(2:1), k(2)(2:2).k(2)(2:)n for the dimers, allow one to describe the overall catalytic profile in terms of the individual contributions. The most catalytically important species are the three dimers La(3+)(2)((-)OCH3)1, La(3+)(2)((-)OCH3)2, and La(3+)(2)((-)OCH3)3. The catalysis of the methanolysis of 2 is spectacular: a 2 x 10(-3) M solution of [La(3+)](total), at neutral, affords a 10(9)-fold acceleration relative to the base reaction (t(1/2) approximately 20 s at 8.2) with excellent turnover. A mechanism of the catalyzed reaction involving the La(3+)(2)((-)OCH3)2 species is proposed.     

Scandium ion-enhanced oxidative dimerization and N-demethylation of N,N-dimethylanilines by a non-heme iron(IV)-oxo complex

Oxidative dimerization of N,N-dimethylaniline (DMA) occurs with a nonheme iron(IV)-oxo complex, [Fe(IV)(O)(N4Py)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), to yield the corresponding dimer, tetramethylbenzidine (TMB), in acetonitrile. The rate of the oxidative dimerization of DMA by [Fe(IV)(O)(N4Py)](2+) is markedly enhanced by the presence of scandium triflate, Sc(OTf)(3) (OTf = CF(3)SO(3)(-)), when TMB is further oxidized to the radical cation (TMB(?+)). In contrast, we have observed the oxidative N-demethylation with para-substituted DMA substrates, since the position of the C-C bond formation to yield the dimer is blocked. The rate of the oxidative N-demethylation of para-substituted DMA by [Fe(IV)(O)(N4Py)](2+) is also markedly enhanced by the presence of Sc(OTf)(3). In the case of para-substituted DMA derivatives with electron-donating substituents, radical cations of DMA derivatives are initially formed by Sc(3+) ion-coupled electron transfer from DMA derivatives to [Fe(IV)(O)(N4Py)](2+), giving demethylated products. Binding of Sc(3+) to [Fe(IV)(O)(N4Py)](2+) enhances the Sc(3+) ion-coupled electron transfer from DMA derivatives to [Fe(IV)(O)(N4Py)](2+), whereas binding of Sc(3+) to DMA derivatives retards the electron-transfer reaction. The complicated kinetics of the Sc(3+) ion-coupled electron transfer from DMA derivatives to [Fe(IV)(O)(N4Py)](2+) are analyzed by competition between binding of Sc(3+) to DMA derivatives and to [Fe(IV)(O)(N4Py)](2+). The binding constants of Sc(3+) to DMA derivatives increase with the increase of the electron-donating ability of the para-substituent. The rate constants of Sc(3+) ion-coupled electron transfer from DMA derivatives to [Fe(IV)(O)(N4Py)](2+), which are estimated from the binding constants of Sc(3+) to DMA derivatives, agree well with those predicted from the driving force dependence of the rate constants of Sc(3+) ion-coupled electron transfer from one-electron reductants to [Fe(IV)(O)(N4Py)](2+). Thus, oxidative dimerization of DMA and N-demethylation of para-substituted DMA derivatives proceed via Sc(3+) ion-coupled electron transfer from DMA derivatives to [Fe(IV)(O)(N4Py)](2+).     

Mechanisms of electron-transfer oxidation of NADH analogues and chemiluminescence. Detection of the keto and enol radical cations

The radical cation of an NADH analogue (BNAH: 1-benzyl-1,4-dihydronicotinamide) has been successfully detected as the transient absorption and ESR spectra in the thermal electron transfer from BNAH to Fe(bpy)(3)(3+) (bpy = 2,2'-bipyridine) and Ru(bpy)(3)(3+). The ESR spectra of the radical cations of BNAH and the dideuterated compound (BNAH-4,4'-d(2)) indicate that the observed radical cation is the keto form rather than the enol form in the tautomerization. The deprotonation rate and the kinetic isotope effects of the keto form of BNAH(*)(+) were determined from the kinetic analysis of the electron-transfer reactions. In the case of electron transfer from BNAH to Ru(bpy)(3)(3+), the chemiluminescence due to Ru(bpy)(3)(2+) was observed in the second electron-transfer step from BNA(*), produced by the deprotonation of the keto form of BNAH(*)(+), to Ru(bpy)(3)(3+). The observation of chemiluminescence due to Ru(bpy)(3)(2+) provides compelling evidence that the Marcus inverted region is observed even for such an intermolecular electron-transfer reaction. When BNAH is replaced by 4-tert-butylated BNAH (4-t-BuBNAH), no chemiluminescence due to Ru(bpy)(3)(2+) has been observed in the electron transfer from 4-t-BuBNAH to Ru(bpy)(3)(3+). This is ascribed to the facile C-C bond cleavage in 4-t-BuBNAH(*)(+). In the laser flash photolysis of a deaerated MeCN solution of BNAH and CHBr(3), the transient absorption spectrum of the enol form of BNAH(*)(+) was detected instead of the keto form of BNAH(*)(+), and the enol form was tautomerized to the keto form. The rate of intramolecular proton transfer in the enol form to produce the keto form of BNAH(*)(+) was determined from the decay of the absorption band due to the enol form and the rise in the absorption band due to the keto form. The kinetic isotope effects were observed for the intramolecular proton-transfer process in the keto form to produce the enol form.     

Transition metal complexes coordinated by an NAD(P)H model compound and their enhanced hydride-donating abilities in the presence of a base

The ruthenium(II) and rhenium(I) complexes containing an NAD(P)H model compound, 1-benzyl-1,4-dihydronicotinamide (BNAH), as ligand, [Ru(tpy)(bpy)(BNAH)]2+ (1 a) and [Re(bpy)(CO)3(BNAH)]+ (1 b), were quantitatively produced by the reaction of the corresponding metal hydrido complexes with BNA(+) (1-benzylnicotinamidium cation). In the presence of base with pK(a) = 8.9, 1 a and 1 b have much greater reducing power than "free" BNAH. The oxidation potentials of 1 a in the absence and the presence of triethylamine were 0.55 V and -0.04 V, respectively, versus Ag/AgNO(3), whereas that of "free" BNAH was 0.30 V. Spectroscopic results clearly showed that the base extracts a proton from the carbamoyl group on 1 a and 1 b to give the deprotonated BNAH coordinating to the transition-metal complexes [Ru(tpy)(bpy)(BNAH-H+)]+ (3 a) and [Re(bpy)(CO)3(BNAH-H+)] (3 b); this deprotonation underlies the enhancement in reducing ability. The deprotonated forms 3 a and 3 b can efficiently reduce other NAD(P) models to give the corresponding 1,4-dihydro form, resulting in the deprotonated BNA+ being coordinated to the metal complexes [Ru(tpy)(bpy)(BNA(+)-H+)]2+ (2 a) and [Re(bpy)(CO)3(BNA+-H+)]+ (2 b); "free" BNAH and the protonated adducts 1 a and 1 b cannot act in this way. X-ray crystallography was performed on the PF6- salt of 2 a, and showed that the deprotonated nitrogen atom on the carbamoyl group coordinates to the ruthenium(II) metal center with a bond length of 2.086(3) Angstroms. Infrared spectral data suggested that the deprotonated carbamoyl group on the reduced forms 3 a and 3 b is converted to the imido group, and that the oxygen atom coordinates to the metal center.     

La3+-catalyzed methanolysis of N-aryl-beta-lactams and nitrocefin

The kinetics of the La(3+)-catalyzed methanolysis of N-phenyl-beta-lactam (2) and N-p-nitrophenyl-beta-lactam (3) as well as that of nitrocefin (1) were studied at 25 degrees C under buffered conditions. In the case of 2 and 3, the observed second-order rate constants (k(2)(obs)) for catalysis plateau at pH 7.5-7.8, reaching values of 1 x 10(-)(2) and 35 x 10(-)(2) M(-)(1) s(-)(1) respectively. Potentiometric titrations of solutions of 2 x 10(-)(3) M La(OTf)(3) were analyzed in terms of a dimer model (La(3+)(2)((-)OCH(3))(n)()), where the number of methoxides varies from 1 to 5. The species responsible for catalysis in the pH range investigated contain 1-3 methoxides, the one having the highest catalytic activity being La(3+)(2)((-)OCH(3))(2), which comprises 80% of the total La(3+) forms present at its pH maximum of 8.9. The catalysis afforded by the La(3+) dimers at a neutral pH is impressive relative to the methoxide reactions: at pH 8.4 a 1 mM solution of catalyst (generated from 2 mM La(OTf)(3)) accelerated the methanolysis of 2 by approximately 2 x 10(7)-fold and 3 by approximately 5 x 10(5)-fold. As a function of metal ion concentration, the La(3+)-catalyzed methanolysis of 1 proceeds by pathways involving first one bound metal ion and then a second La(3+) leading to a plateau in the k(obs) vs [La(3+)](total) plots at all pH values. The k(max)(obs) pseudo-first-order rate constants at the plateaus, representing the spontaneous methanolysis of La(3+)(2)(1(-)) forms, has a linear dependence on [(-)OCH(3)] (slope = 0.84 +/- 0.05 if all pH values are used and 1.02 +/- 0.03 if all but the two highest pH values are used). The speciation of bound 1 at a La(3+) concentrations corresponding to that of the onset of the kinetic plateau region was approximated through potentiometric titration of the nonreactive 3,5-dinitrobenzoic acid in the presence of 2 equiv of La(OTf)(3). A total speciation diagram for all bound forms of La(3+)(2)(1(-))((-)OCH(3))(n)(), where n = 0-5, was constructed and used to determine their kinetic contributions to the overall pH vs k(max)(obs) plot under kinetic conditions. Two kinetically equivalent mechanisms were analyzed: methoxide attack on La(3+)(2)(1(-))((-)OCH(3))(n)(), n = 0-2; unimolecular decomposition of the forms La(3+)(2)(1(-))((-)OCH(3))(n)(), n = 1-3.     

Scandium ion-promoted photoinduced electron-transfer oxidation of fullerenes and derivatives by p-chloranil and p-benzoquinone.

In the presence of scandium triflate, an efficient photoinduced electron transfer from the triplet excited state of C(60) to p-chloranil occurs to produce C(60) radical cation which has a diagnostic NIR (near-infrared) absorption band at 980 nm, whereas no photoinduced electron transfer occurs from the triplet excited state of C(60) (3C(60)) to p-chloranil in the absence of scandium ion in benzonitrile. The electron-transfer rate obeys pseudo-first-order kinetics and the pseudo-first-order rate constant increases linearly with increasing p-chloranil concentration. The observed second-order rate constant of electron transfer (k(et)) increases linearly with increasing scandium ion concentration. In contrast to the case of the C(60)/p-chloranil/Sc(3+) system, the k(et) value for electron transfer from 3C(60) to p-benzoquinone increases with an increase in Sc(3+) concentration ([Sc(3+)]) to exhibit a first-order dependence on [Sc(3+)], changing to a second-order dependence at the high concentrations. Such a mixture of first-order and second-order dependence on [Sc(3+)] is also observed for a Sc(3+)-promoted electron transfer from CoTPP (TPP(2-) = tetraphenylporphyrin dianion) to p-benzoquinone. This is ascribed to formation of 1:1 and 1:2 complexes between the generated semiquinone radical anion and Sc(3+) at the low and high concentrations of Sc(3+), respectively. The transient absorption spectra of the radical cations of various fullerene derivatives were detected by laser flash photolysis of the fullerene/p-chloranil/Sc(3+) systems. The ESR spectra of the fullerene radical cations were also detected in frozen PhCN at 193 K under photoirradiation of the fullerene/p-chloranil/Sc(3+) systems. The Sc(3+)-promoted electron-transfer rate constants were determined for photoinduced electron transfer from the triplet excited states of C(60), C(70), and their derivatives to p-chloranil and the values are compared with the HOMO (highest occupied molecular orbital) levels of the fullerenes and their derivatives.     

Accelerating and decelerating effects of metal ions on electron-transfer reduction of quinones as a function of temperature and binding modes of metal ions to semiquinone radical anions

The accelerating effect of Sc(3+) on the electron-transfer (ET) reduction of the p-benzoquinone derivative 1-(p-tolylsulfinyl)-2,5-benzoquinone (TolSQ) by 10,10'-dimethyl-9,9'-biacridine ((AcrH)(2)) at 233 K changes to a decelerating effect with increasing reaction temperature; the observed second-order rate constant k(et) decreases with increasing Sc(3+) concentration at high concentrations of Sc(3+) at 298 K. At 263 K the k(et) value remains constant with increasing Sc(3+) concentration. Such a remarkable difference with regard to dependence of k(et) on [Sc(3+)] between low and high temperatures results from the difference in relative activity of two ET pathways that depend on temperature, one of which affords 1:1 complex TolSQ*(-)-Sc(3+), and the other 1:2 complex TolSQ*(-)-(Sc(3+))(2) with additional binding of Sc(3+) to TolSQ*(-)-Sc(3+). The formation of TolSQ*(-)-Sc(3+) and TolSQ*(-)-(Sc(3+))(2) complexes was confirmed by EPR spectroscopy in the ET reduction of TolSQ in the presence of low and high concentrations of Sc(3+), respectively. The effects of metal ions on other ET reactions of quinones to afford 1:1 and 1:2 complexes between semiquinone radical anions and metal ions are also reported. The ET pathway affording the 1:2 complexes has smaller activation enthalpies DeltaH( not equal) and more negative activation entropies DeltaS( not equal) because of stronger binding of metal ions and more restricted geometries of the ET transition states as compared with the ET pathway to afford the 1:1 complexes.     

Binding modes in metal ion complexes of quinones and semiquinone radical anions: electron-transfer reactivity.

9,10-Phenanthrenequinone (PQ) and 1,10-phenanthroline-5,6-dione (PTQ) form 1:1 and 2:1 complexes with metal ions (M (n+)=Sc (3+), Y (3+), Mg (2+), and Ca (2+)) in acetonitrile (MeCN), respectively. The binding constants of PQ--M (n+) complexes vary depending on either the Lewis acidity or ion radius of metal ions. The one-electron reduced species (PTQ(-)) forms 1:1 complexes with M (n+), and PQ(-) also forms 1:1 complexes with Sc(3+), Mg(2+), and Ca(2+), whereas PQ(-) forms 1:2 complexes with Y(3+) and La(3+), as indicated by electron spin resonance (ESR) measurements. On the other hand, semiquinone radical anions (Q(-) and NQ(-)) derived from p-benzoquinone (Q) and 1,4-naphthoquinone (NQ) form Sc(3+)-bridged pi-dimer radical anion complexes, Q(-)--(Sc(3+))(n)--Q and NQ(-)--(Sc(3+))(n)-NQ (n=2 and 3), respectively. The one-electron reduction potentials of quinones (PQ, PTQ, and Q) are largely positively shifted in the presence of M (n+). The rate constant of electron transfer from CoTPP (TPP(2-)=dianion of tetraphenylporphyrin) to PQ increases with increasing the concentration of Sc(3+) to reach a constant value, when all PQ molecules form the 1:1 complex with Sc(3+). Rates of electron transfer from 10,10'-dimethyl-9,9'-biacridine [(AcrH)(2)] to PTQ are also accelerated significantly by the presence of Sc(3+), Y(3+), and Mg(2+), exhibiting a first-order dependence with respect to concentrations of metal ions. In contrast to the case of o-quinones, unusually high kinetic orders are observed for rates of Sc(3+)-promoted electron transfer from tris(2-phenylpyridine)iridium(III) [Ir(ppy)(3)] to p-quinones (Q): second-order dependence on concentration of Q, and second- and third-order dependence on concentration of Sc(3+) due to formation of highly ordered radical anion complexes, Q()--(Sc(3+))(n)--Q (n=2 and 3).     

La(3+)-Catalyzed methanolysis of hydroxypropyl-p-nitrophenyl phosphate as a model for the RNA transesterification reaction

The methanolysis of hydroxypropyl-p-nitrophenyl phosphate (HPNPP, 1) promoted by La(OTf)(3) under buffered conditions was studied in methanol as a function of pH at 25 degrees C. (31)P NMR studies at -90 degrees C indicate that there are at least three La/1 complexes formed at pH approximately 5.3 of 1:1, 2:2, and 1:2 stoichiometry. Kinetic studies of the observed pseudo-first-order rate constants for the methanolysis of 1 as a function of [La(3+)] at 4.5 < pH < 10.5 indicate there are two general pH regimes. In the low pH regime between 4.5 and 7.6, the plots of k(obs) versus [La(3+)] exhibit saturation behavior with very strong 1:1 binding, with a plateau rate constant that depends on [OCH(3)(-)]. The catalytically productive species is shown to be a 2:2 complex of La(3+) and 1, where the phosphate is proposed to be doubly activated, thereby promoting the methoxide reaction by some 4.6 x 10(10)-fold. In the high pH regime from 7.9 to 10.5, 1:1, 2:2, and 2:1 La(3+)/1 complexes are formed with the La(3+) coordinated in the form of [La(3+)(OCH(3)(-))](1,2). Throughout this pH regime at high [La(3+)], a saturation complex, (La(3+)OCH(3)(-))(2)/1, is formed that spontaneously decomposes with a rate constant of (5-10) x 10(-)(3) s(-)(1), leading to an acceleration of 10(9)-fold at pH 8.0.     

Proton-promoted oxygen atom transfer vs proton-coupled electron transfer of a non-heme iron(IV)-oxo complex

Sulfoxidation of thioanisoles by a non-heme iron(IV)-oxo complex, [(N4Py)Fe(IV)(O)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), was remarkably enhanced by perchloric acid (70% HClO(4)). The observed second-order rate constant (k(obs)) of sulfoxidation of thioaniosoles by [(N4Py)Fe(IV)(O)](2+) increases linearly with increasing concentration of HClO(4) (70%) in acetonitrile (MeCN)at 298 K. In contrast to sulfoxidation of thioanisoles by [(N4Py)Fe(IV)(O)](2+), the observed second-order rate constant (k(et)) of electron transfer from one-electron reductants such as [Fe(II)(Me(2)bpy)(3)](2+) (Me(2)bpy = 4,4-dimehtyl-2,2'-bipyridine) to [(N4Py)Fe(IV)(O)](2+) increases with increasing concentration of HClO(4), exhibiting second-order dependence on HClO(4) concentration. This indicates that the proton-coupled electron transfer (PCET) involves two protons associated with electron transfer from [Fe(II)(Me(2)bpy)(3)](2+) to [(N4Py)Fe(IV)(O)](2+) to yield [Fe(III)(Me(2)bpy)(3)](3+) and [(N4Py)Fe(III)(OH(2))](3+). The one-electron reduction potential (E(red)) of [(N4Py)Fe(IV)(O)](2+) in the presence of 10 mM HClO(4) (70%) in MeCN is determined to be 1.43 V vs SCE. A plot of E(red) vs log[HClO(4)] also indicates involvement of two protons in the PCET reduction of [(N4Py)Fe(IV)(O)](2+). The PCET driving force dependence of log k(et) is fitted in light of the Marcus theory of outer-sphere electron transfer to afford the reorganization of PCET (λ = 2.74 eV). The comparison of the k(obs) values of acid-promoted sulfoxidation of thioanisoles by [(N4Py)Fe(IV)(O)](2+) with the k(et) values of PCET from one-electron reductants to [(N4Py)Fe(IV)(O)](2+) at the same PCET driving force reveals that the acid-promoted sulfoxidation proceeds by one-step oxygen atom transfer from [(N4Py)Fe(IV)(O)](2+) to thioanisoles rather than outer-sphere PCET.     

Mechanistic borderline between one-step hydrogen transfer and sequential transfers of electron and proton in reactions of NADH analogues with triplet excited states of tetrazines and Ru(bpy)(3)2+

Efficient energy transfer from Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine, denotes the excited state) to 3,6-disubstituted tetrazines [R(2)Tz: R = Ph (Ph(2)Tz), 2-chlorophenyl [(ClPh)(2)Tz], 2-pyridyl (Py(2)Tz)] occurs to yield the triplet excited states of tetrazines ((3)R(2)Tz(*)), which have longer lifetimes and higher oxidizing ability as compared with those of Ru(bpy)(3)(2+). The dynamics of hydrogen-transfer reactions from NADH (dihydronicotinamide adenine dinucleotide) analogues has been examined in detail using (3)R(2)Tz(*) by laser flash photolysis measurements. Whether formal hydrogen transfer from NADH analogues to (3)R(2)Tz(*) proceeds via a one-step process or sequential electron and proton transfer processes is changed by a subtle difference in the electron donor ability and the deprotonation reactivity of the radical cations of NADH analogues as well as the electron-acceptor ability of (3)R(2)Tz(*) and the protonation reactivity of R(2)Tz(*)(-). In the case of (3)Ph(2)Tz(*), which is a weaker electron acceptor than the other tetrazine derivatives [(ClPh)(2)Tz; Py(2)Tz], direct one-step hydrogen transfer occurs from 10-methyl-9,10-dihydroacridine (AcrH(2)) to (3)Ph(2)Tz(*) without formation of the radical cation (AcrH(2)(*)(+)). The rate constant of the direct hydrogen transfer from AcrH(2) to (3)Ph(2)Tz(*) is larger than that expected from the Gibbs energy relation for the rate constants of electron transfer from various electron donors to (3)Ph(2)Tz(*), exhibiting the primary deuterium kinetic isotope effect. On the other hand, hydrogen transfer from 9-isopropyl-10-methyl-9,10-dihydroacridine (AcrHPr(i)) and 1-benzyl-1,4-dihydronicotinamide (BNAH) to (3)R(2)Tz(*) occurs via sequential electron and proton transfer processes, when both the radical cations and deprotonated radicals of NADH analogues are detected by the laser flash photolysis measurements.     

Oxidations of NADH analogues by cis-[RuIV(bpy)2(py)(O)]2+ occur by hydrogen-atom transfer rather than by hydride transfer

Oxidations of the NADH analogues 10-methyl-9,10-dihydroacridine (AcrH2) and N-benzyl 1,4-dihydronicotinamide (BNAH) by cis-[RuIV(bpy)2(py)(O)]2+ (RuIVO2+) have been studied to probe the preferences for hydrogen-atom transfer vs hydride transfer mechanisms for the C-H bond oxidation. 1H NMR spectra of completed reactions of AcrH2 and RuIVO2+, after more than approximately 20 min, reveal the predominant products to be 10-methylacridone (AcrO) and cis-[RuII(bpy)2(py)(MeCN)]2+. Over the first few seconds of the reaction, however, as monitored by stopped-flow optical spectroscopy, the 10-methylacridinium cation (AcrH+) is observed. AcrH+ is the product of net hydride removal from AcrH2, but hydride transfer cannot be the dominant pathway because AcrH+ is formed in only 40-50% yield and its subsequent oxidation to AcrO is relatively slow. Kinetic studies show that the reaction is first order in both RuIVO2+ and AcrH2, with k = (5.7 +/- 0.3) x 10(3) M(-1) s(-1) at 25 degrees C, DeltaH(double dagger) = 5.3 +/- 0.3 kcal mol(-1) and DeltaS(double dagger) = -23 +/- 1 cal mol(-1) K(-1). A large kinetic isotope effect is observed, kAcrH2/kAcrD2 = 12 +/- 1. The kinetics of this reaction are significantly affected by O2. The rate constants for the oxidations of AcrH2 and BNAH correlate well with those for a series of hydrocarbon C-H bond oxidations by RuIVO2+. The data indicate a mechanism of initial hydrogen-atom abstraction. The acridinyl radical, AcrH*, then rapidly reacts by electron transfer (to give AcrH+) or by C-O bond formation (leading to AcrO). Thermochemical analyses show that H* and H- transfer from AcrH2 to RuIVO2+ are comparably exoergic: DeltaG degrees = -10 +/- 2 kcal mol(-1) (H*) and -6 +/- 5 kcal mol(-1) (H-). That a hydrogen-atom transfer is preferred kinetically suggests that this mechanism has an equal or lower intrinsic barrier than a hydride transfer pathway.     

Cupric superoxo-mediated intermolecular C-H activation chemistry

The new cupric superoxo complex [LCu(II)(O(2)(?-))](+), which possesses particularly strong O-O and Cu-O bonding, is capable of intermolecular C-H activation of the NADH analogue 1-benzyl-1,4-dihydronicotinamide (BNAH). Kinetic studies indicated a first-order dependence on both the Cu complex and BNAH with a deuterium kinetic isotope effect (KIE) of 12.1, similar to that observed for certain copper monooxygenases.     

Effects of metal ions on photoinduced electron transfer in zinc porphyrin-naphthalenediimide linked systems

Zinc porphyrin-naphthalenediimide (ZnP-NIm) dyads and zinc porphyrin-pyromellitdiimide-naphthalenediimide (ZnP-Im-NIm) triad have been employed to examine the effects of metal ions on photoinduced charge-separation (CS) and charge-recombination (CR) processes in the presence of metal ions (scandium triflate (Sc(OTf)(3)) or lutetium triflate (Lu(OTf)(3)), both of which can bind with the radical anion of NIm). Formation of the charge-separated states in the absence and in the presence of Sc(3+) was confirmed by the appearance of absorption bands due to ZnP(.) (+) and NIm(.) (-) in the absence of metal ions and of those due to ZnP(.) (+) and the NIm(.) (-)/Sc(3+) complex in the presence of Sc(3+) in the time-resolved transient absorption spectra of dyads and triad. The lifetimes of the charge-separated states in the presence of 1.0 x 10(-3) M Sc(3+) (14 micros for ZnP-NIm, 8.3 micros for ZnP-Im-NIm) are more than ten times longer than those in the absence of metal ions (1.3 micros for ZnP-NIm, 0.33 micros for ZnP-Im-NIm). In contrast, the rate constants of the CS step determined by the fluorescence lifetime measurements are the same, irrespective of the presence or absence of metal ions. This indicates that photoinduced electron transfer from (1)ZnP(*) to NIm in the presence of Sc(3+) occurs without involvement of the metal ion to produce ZnP(.) (+)-NIm(.) (-), followed by complexation with Sc(3+) to afford the ZnP(.) (+)-NIm(.) (-)/Sc(3+) complex. The one-electron reduction potential (E(red)) of the NIm moiety in the presence of a metal ion is shifted in a positive direction with increasing metal ion concentration, obeying the Nernst equation, whereas the one-electron oxidation potential of the ZnP moiety remains the same. The driving force dependence of the observed rate constants (k(ET)) of CS and CR processes in the absence and in the presence of metal ions is well evaluated in terms of the Marcus theory of electron transfer. In the presence of metal ions, the driving force of the CS process is the same as that in the absence of metal ions, whereas the driving force of the CR process decreases with increasing metal ion concentration. The reorganization energy of the CR process also decreases with increasing metal ion concentration, when the CR rate constant becomes independent of the metal ion concentration.     

Electron donor-acceptor dyads and triads based on tris(bipyridine)ruthenium(II) and benzoquinone: synthesis,characterization, and photoinduced electron transfer reactions

Two electron donor-acceptor triads based on a benzoquinone acceptor linked to a light absorbing [Ru(bpy)(3)](2+) complex have been synthesized. In triad 6 (denoted Ru(II)-BQ-Co(III)), a [Co(bpy)(3)](3+) complex, a potential secondary acceptor, was linked to the quinone. In the other triad, 8 (denoted PTZ-Ru(II)-BQ), a phenothiazine donor was linked to the ruthenium moiety. The corresponding dyads Ru(II)-BQ (4) and PTZ-Ru(II) (9) were prepared for comparison. Upon light excitation in the visible band of the ruthenium moiety, electron transfer to the quinone occurred with a rate constant k(f) = 5 x 10(9) s(-)(1) (tau(f) = 200 ps) in all the quinone containing complexes. Recombination to the ground state followed, with a rate constant k(b) approximately 4.5 x 10(8) s(-)(1) (tau(b) approximately 2.2 ns), for both Ru(II)-BQ and Ru(II)-BQ-Co(III) with no indication of a charge shift to generate the reduced Co(II) moiety. In the PTZ-Ru(II)-BQ triad, however, the initial charge separation was followed by a rapid (k > 5 x 10(9) s(-)(1)) electron transfer from the phenothiazine moiety to give the fairly long-lived PTZ(*)(+)-Ru(II)-BQ(*)(-) state (tau = 80 ns) in unusually high yield for a [Ru(bpy)(3)](2+)-based triad (> 90%), that lies at DeltaG degrees = 1.32 eV relative to the ground state. Unfortunately, this triad turned out to be rather photolabile. Interestingly, coupling between the oxidized PTZ(*)(+) and the BQ(*)(-) moieties seemed to occur. This discouraged further extension to incorporate more redox active units. Finally, in the dyad PTZ-Ru(II) a reversible, near isoergonic electron transfer was observed on excitation. Thus, a quasiequilibrium was established with an observed time constant of 7 ns, with ca. 82% of the population in the PTZ-Ru(II) state and 18% in the PTZ(*)(+)-Ru(II)(bpy(*)(-)) state. These states decayed in parallel with an observed lifetime of 90 ns. The initial electron transfer to form the PTZ(*)(+)-Ru(II)(bpy(*)(-)) state was thus faster than what would have been inferred from the Ru(II) emission decay (tau = 90 ns). This result suggests that reports for related PTZ-Ru(II) and PTZ-Ru(II)-acceptor complexes in the literature might need to be reconsidered.     

Stepwise vs. concerted pathways in scandium ion-coupled electron transfer from superoxide ion to p-benzoquinone derivatives

Superoxide ion (O2˙-) forms a stable 1 : 1 complex with scandium hexamethylphosphoric triamide complex [Sc(HMPA)(3)(3+)], which can be detected in solution by ESR spectroscopy. Electron transfer from O2˙- -Sc(HMPA)(3)(3+) complex to a series of p-benzoquinone derivatives occurs, accompanied by binding of Sc(HMPA)(3)(3+) to the corresponding semiquinone radical anion complex to produce the semiquinone radical anion-Sc(HMPA)(3)(3+) complexes. The 1 : 1 and 1 : 2 complexes between semiquinone radical anions and Sc(HMPA)(3)(3+) depending on the type of semiquinone radical anions were detected by ESR measurements. This is defined as Sc(HMPA)(3)(3+)-coupled electron transfer. There are two reaction pathways in the Sc(HMPA)(3)(3+)-coupled electron transfer. One is a stepwise pathway in which the binding of Sc(HMPA)(3)(3+) to semiquinone radical anions occurs after the electron transfer, when the rate of electron transfer remains constant with the change in concentration of Sc(HMPA)(3)(3+). The other is a concerted pathway in which electron transfer and the binding of Sc(HMPA)(3)(3+) occurs in a concerted manner, when the rates of electron transfer exhibit first-order and second-order dependence on the concentration of Sc(HMPA)(3)(3+) depending the number of Sc(HMPA)(3)(3+) (one and two) bound to semiquinone radical anions. The contribution of two pathways changes depending on the substituents on p-benzoquinone derivatives. The present study provides the first example to clarify the kinetics and mechanism of metal ion-coupled electron-transfer reactions of the superoxide ion.