Influence of the electronics of the phosphine ligands on the H-H bond elongation in dihydrogen complexes

Five new monocationic dihydrogen complexes of ruthenium of the type trans-[RuCl(eta(2)-H(2))(PP)(2)][BF(4)] (PP = bis-1,2(diarylphosphino)ethane, aryl = p-fluorobenzyl, 1a, benzyl, 2a, m-methylbenzyl, 3a, p-methylbenzyl, 4a, p-isopropylbenzyl, 5a) have been prepared by protonating the precursor hydride complexes trans-[RuCl(H)(PP)(2)] using HBF(4).OEt(2). The dihydrogen complexes are quite stable and have been isolated in the solid state. The intact nature of the H-H bond in these derivatives has been established from the short spin-lattice relaxation times (T1, ms) and observation of substantial H, D couplings in the HD isotopomers. The H-H bond distances (dHH, A) increase systematically from 0.97 to 1.03 A as the electron-donor ability of the substituent on the diphosphine ligand increases from the p-fluorobenzyl to the p-isopropylbenzyl moiety. The d(HH) in trans-[Ru(eta(2)-H(2))(Cl)((C(6)H(5)CH(2))(2)PCH(2)CH(2)P(CH(2)C(6)H(5))(2))(2)][BF(4)], 2a, was found to be 1.08(5) A by X-ray crystallography. In addition, two new 16-electron dicationic dihydrogen complexes of the type [Ru(eta(2)-H(2))(PP)(2)][OTf](2) (PP = (ArCH(2))(2)PCH(2)CH(2)P(CH(2)Ar)(2), Ar = m-CH(3)C(6)H(4-), 6a, p-CH(3)C(6)H(4)-, 7a) have also been prepared and characterized. These derivatives were found to possess elongated dihydrogen ligands.     

Revelation of the nature of the reducing species in titanocene halide-promoted reductions

The fundamental nature of Ti(III) complexes generated in tetrahydrofuran by reduction of Cp(2)TiCl(2) has been clarified by means of cyclic voltammetry and kinetic measurements. While the electrochemical reduction of Cp(2)TiCl(2) leads to the formation of Cp(2)TiCl(2)(-), the use of metals such as Zn, Al, or Mn as reductants affords Cp(2)TiCl and (Cp(2)TiCl)(2) in a mixture having a dimerization equilibrium constant of 3 x 10(3) M(-)(1), independent of the metal used. Thus, we find it unlikely that the trinuclear complexes or ionic clusters known from the solid phase should be present in solution as previously suggested. The standard potentials determined for the redox couples Cp(2)TiCl(2)/Cp(2)TiCl(2)(-), (Cp(2)TiCl)(2)(+)/(Cp(2)TiCl)(2), Cp(2)TiCl(+)/Cp(2)TiCl, and Cp(2)Ti(2+)/Cp(2)Ti(+) increase in the order listed. However, the reactivity of the different Ti(III) complexes is assessed as (Cp(2)TiCl)(2) greater, similar Cp(2)TiCl approximately Cp(2)Ti(+) > Cp(2)TiCl(2)(-) in their reactions with benzyl chloride and benzaldehyde. None of the reactions proceed by an outer-sphere electron transfer pathway, and clearly the inner-sphere character is much higher in the case of Cp(2)Ti(+) than for (Cp(2)TiCl)(2), Cp(2)TiCl, and in particular Cp(2)TiCl(2)(-). As to the electron acceptor, the inner-sphere character increases, going from benzyl chloride to benzaldehyde, and it is suggested that the chlorine atom in benzyl chloride and the oxygen atom in benzaldehyde may function as bridges between the reactants in the transition state.     

Influence of chirality of the preceding acyl moiety on the cis/trans ratio of the proline peptide bond

We report that the cis/trans ratio of the proline peptide bond can be strongly influenced by the chirality of the acyl residue preceding proline. Acyl moieties derived from (2S)-2,6-dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylic acid (8) and (2R)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoic acid (5) in acyl-Pro molecules influence isomerization of the proline peptide bond constraining the omega dihedral angle to the trans orientation. Structures of benzyl (2S)-1-([(2S)-2,6-dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-2-yl]carbonyl)-2-pyrrolidinecarboxylate (3) derived from 2D (1)H NMR conformational analysis and crystallographic data exhibit only the trans conformation of proline peptide bond. On the other hand the diastereomer 4, which contains an (R) acyl moiety, exhibits two sets of signals in (1)H NMR spectra. The signals were assigned to trans (72%) and cis (28%) conformers. Crystallographic analysis of 4 showed that only the cis conformation is present in the crystalline state. The (1)H NMR chemical shift pattern of three sets of signals observed in 2 was observed also in benzyl (2S)-1-[(2R/S)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoyl]-2-pyrrolidinecarboxylate. (R)-Carboxylic acid 5, after coupling with (S)-ProOBn, yielded benzyl (2S)-1-[(2R)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoyl]-2-pyrrolidinecarboxylate (6), which in DMSO-d(6) exhibited only the trans conformation of the proline peptide bond. These results suggest that in these particular cases acyl-Pro peptide bond isomerization is strongly influenced by the stereochemistry of the acyl residue preceding proline. (2S)-2,6-Dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylic acid (8) and (2R)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoic acid (5) are promising chiral peptidomimetic building blocks that can be used as acyl moieties to force the proline peptide bond into the trans conformation in a variety of acyl-Pro molecules.     

Computational study of the reaction mechanism of the methylperoxy self-reaction

To provide insight on the reaction mechanism of the methyperoxy (CH(3)O(2)?) self-reaction, stationary points on both the spin-singlet and the spin-triplet potential energy surfaces of 2(CH(3)O(2)?) have been searched at the B3LYP/6-311++G(2df,2p) level. The relative energies, enthalpies, and free energies of these stationary points are calculated using CCSD(T)/cc-pVTZ. Our theoretical results indicate that reactions on a spin-triplet potential energy surface are kinetically unfavorable due to high free energy barriers, while they are more complicated on the spin-singlet surface. CH(3)OOCH(3) + O(2)(1) can be produced directly from 2(CH(3)O(2)?), while in other channels, three spin-singlet chain-structure intermediates are first formed and subsequently dissociated to produce different products. Besides the dominant channels producing 2CH(3)O? + O(2) and CH(3)OH + CH(2)O + O(2) as determined before, the channels leading to CH(3)OOOH + CH(2)O and CH(3)O? + CH(2)O + HO(2)? are also energetically favorable in the self-reaction of CH(3)O(2)? especially at low temperature according to our results.     

Predicting the energy of the water exchange reaction and free energy of solvation for the uranyl ion in aqueous solution

The structures and vibrational frequencies of UO2(H2O)4(2+) and UO2(H2O)5(2+) have been calculated using density functional theory and are in reasonable agreement with experiment. The energies of various reactions were calculated at the density functional theory (DFT) and MP2 levels; the latter provides the best results. Self-consistent reaction field calculations in the PCM and SCIPCM approximations predicted the free energy of the water exchange reaction, UO2(H2O)4(2+) + H2O <--> UO2(H2O)5(2+). The calculated free energies of reaction are very sensitive to the choice of radii (O and H) and isodensity values in the PCM and SCIPCM models, respectively. Results consistent with the experimental HEXS value of -1.19 +/- 0.42 kcal/mol (within 1-3 kcal/mol) are obtained with small cavities. The structures and vibrational frequencies of the clusters with second solvation shell waters: UO2(H2O)4(H2O)8(2+), UO2(H2O)4(H2O)10(2+), UO2(H2O)4(H2O)11(2+), UO2(H2O)5(H2O)7(2+), and UO2(H2O)5(H2O)10(2+), were calculated and are in better agreement with experiment as compared to reactions involving only UO2(H2O)4(2+) and UO2(H2O)5(2+). The MP2 reaction energies for water exchange gave gas-phase results that agreed with experiment in the range -5.5 to +3.3 kcal/mol. The results were improved by inclusion of a standard PCM model with differences of -1.2 to +2.7 kcal/mol. Rearrangement reactions based on an intramolecular isomerization leading to a redistribution of water in the two shells provide good values in comparison to experiment with values of Delta G(exchange) from -2.2 to -0.5 kcal/mol so the inclusion of a second hydration sphere accounts for most solvation effects. Calculation of the free energy of solvation of the uranyl cation yielded an upper bound to the solvation energy of -410 +/- 5 kcal/mol, consistent with the best experimental value of -421 +/- 15 kcal/mol.     

Synthesis and reactivity of the imido analogues of the uranyl ion

Addition of 1.5 equiv of I2 to a THF solution of UI3(THF)4, containing either 6 equiv of tBuNH2 or 2 equiv of RNH2 (R = Ph, 3,5-(CF3)2C6H3, 2,6-(iPr)2C6H3) and 4 equiv of NEt3, generates orange solutions containing U(NtBu)2I2(THF)2 (1) or U(NAr)2I2(THF)3 (Ar = Ph, 2; 3,5-(CF3)2C6H3, 3; 2,6-(iPr)2C6H3, 4), respectively, all of which can be isolated in good yields. Alternatively, 1 can be prepared by reaction of uranium metal with 3 equiv of I2 and 6 equiv of tBuNH2, also in good yield. Complexes 1-4 have been characterized by X-ray crystallography, and each of these complexes exhibits linear N-U-N linkages and short U-N bonds. Using density functional theory simulations of complexes 1 and 2, two triple bonds between the metal center and the nitrogen ligands were identified. Complexes 1 and 2 readily react with neutral Lewis bases such as pyridine or Ph3PO to form U(NR)2I2(L)2 (R = tBu, L = py, 5; Ph3PO, 7; R = Ph, L = py, 6; Ph3PO, 8), and with PMe3 to form U(NR)2I2(THF)(PMe3)2 (R = tBu, 9; Ph, 10). The solid-state molecular structures of 5, 7, and 9 have been determined by X-ray crystallography, and these complexes, like their parent compounds, exhibit linear N-U-N angles and short U-N bonds. Complexes 1 and 2 also react with AgOTf in CH2Cl2, forming U(NR)2(OTf)2(THF)3 (R = tBu, 11; Ph, 12) after recrystallization from THF. Crystals of 12 grown from CH2Cl2 were found to contain a dimer, [U(NPh)2(OTf)2(THF)2]2, a complex possessing bridging triflate groups.     

Mechanism of the

Stereochemical studies on [2 + 2] photoaddition of cis-/trans-4-propenylanisole (cis-1 and trans-1) and cis-1-(p-methoxyphenyl)ethylene-2-d(1) (cis-3-d(1)) to C(60) exhibit stereospecificity in favor of the trans-2 cycloadduct in the former case and nonstereoselectivity in the latter. The observed stereoselectivity in favor of the cis-6-d(3) [2 + 2] diastereomer by 12% in the case of the photochemical addition of (E)-1-(p-methoxyphenyl)-2-methyl-prop-1-ene-3,3,3-d(3) (trans-5-d(3)) to C(60) is attributed to a steric kinetic isotope effect (k(H)/k(D) = 0.78). The loss of stereochemistry in the cyclobutane ring excludes a concerted addition and is consistent with a stepwise mechanism. Intermolecular secondary kinetic isotope effects of the [2 + 2] photocycloaddition of 3-d(0) vs 3-d(1), and 3-d(6) as well as 5-d(0) vs 5-d(1), and 5-d(6) to C(60) were also measured. The intermolecular competition due to deuterium substitution of both vinylic hydrogens at the beta-carbon of 3 exhibits a substantial inverse alpha-secondary isotope effect k(H)/k(D) = 0.83 (per deuterium). Substitution with deuterium at both vinylic methyl groups of 5 yields a small inverse k(H)/k(D) = 0. 94. These results are consistent with the formation of an open intermediate in the rate-determining step.     

p-tert-Butylcalix[4]arene complexes of molybdenum and tungsten: reactivity of the calixarene methylene C-H bond and the facile migration of the metal around the phenolic rim of the calixarene

p-tert-Butylcalix[4]arene, [CalixBut(OH)4], reacts with Mo(PMe3)6 and W(PMe3)4(eta2-CH2PMe2)H to yield compounds of composition {[CalixBut(OH)2(O)2]M(PMe3)3H2} which exhibit unprecedented use of a C-H bond of a calixarene methylene group as a binding functionality in the form of agostic and alkyl hydride derivatives. Thus, X-ray diffraction studies demonstrate that, in the solid state, the molybdenum complex [CalixBut(OH)2(O)2]Mo(PMe3)3H2 exists as an agostic derivative with a Mo...H-C interaction, whereas the tungsten complex exists as a metallated trihydride [Calix-HBut(OH)2(O)2]W(PMe3)3H3. Solution 1H NMR spectroscopic studies, however, provide evidence that [Calix-HBut(OH)2(O)2]W(PMe3)3H3 is in equilibrium with its agostic isomer [CalixBut(OH)2(O)2]W(PMe3)3H2. Dynamic NMR spectroscopy also indicates that the [M(PMe3)3H2] fragments of both the molybdenum and tungsten complexes [CalixBut(OH)2(O)2]M(PMe3)3H2 migrate rapidly around the phenolic rim of the calixarene on the NMR time scale, an observation that is in accord with incorporation of deuterium into the methylene endo positions upon treatment of the isomeric mixture of [CalixBut(OH)2(O)2]W(PMe3)3H2 and [Calix-HBut(OH)2(O)2]W(PMe3)3H3 with D2. Treatment of {[CalixBut(OH)2(O)2]W(PMe3)3H2} with Ph2C2 gives the alkylidene complex [CalixBut(O)4]W=C(Ph)Ar [Ar = PhCC(Ph)CH2Ph].     

Stereospecificity of the dehydratase domain of the erythromycin polyketide synthase

The dehydratase (DH) domain of module 4 of the 6-deoxyerythronolide B synthase (DEBS) has been shown to catalyze an exclusive syn elimination/syn addition of water. Incubation of recombinant DH4 with chemoenzymatically prepared anti-(2R,3R)-2-methyl-3-hydroxypentanoyl-ACP (2a-ACP) gave the dehydration product 3-ACP. Similarly, incubation of DH4 with synthetic 3-ACP resulted in the reverse enzyme-catalyzed hydration reaction, giving an ～3:1 equilbrium mixture of 2a-ACP and 3-ACP. Incubation of a mixture of propionyl-SNAC (4), methylmalonyl-CoA, and NADPH with the DEBS β-ketoacyl synthase-acyl transferase [KS6][AT6] didomain, DEBS ACP6, and the ketoreductase domain from tylactone synthase module 1 (TYLS KR1) generated in situ anti-2a-ACP that underwent DH4-catalyzed syn dehydration to give 3-ACP. DH4 did not dehydrate syn-(2S,3R)-2b-ACP, syn-(2R,3S)-2c-ACP, or anti-(2S,3S)-2d-ACP generated in situ by DEBS KR1, DEBS KR6, or the rifamycin synthase KR7 (RIFS KR7), respectively. Similarly, incubation of a mixture of (2S,3R)-2-methyl-3-hydroxypentanoyl-N-acetylcysteamine thioester (2b-SNAC), methylmalonyl-CoA, and NADPH with DEBS [KS6][AT6], DEBS ACP6, and TYLS KR1 gave anti-(2R,3R)-6-ACP that underwent syn dehydration catalyzed by DEBS DH4 to give (4R,5R)-(E)-2,4-dimethyl-5-hydroxy-hept-2-enoyl-ACP (7-ACP). The structure and stereochemistry of 7 were established by GC-MS and LC-MS comparison of the derived methyl ester 7-Me to a synthetic sample of 7-Me.     

Distribution of the cationic state over the chlorophyll pair of the photosystem II reaction center

The reaction center chlorophylls a (Chla) of photosystem II (PSII) are composed of six Chla molecules including the special pair Chla P(D1)/P(D2) harbored by the D1/D2 heterodimer. They serve as the ultimate electron abstractors for water oxidation in the oxygen-evolving Mn(4)CaO(5) cluster. Using the PSII crystal structure analyzed at 1.9 ? resolution, the redox potentials of P(D1)/P(D2) for one-electron oxidation (E(m)) were calculated by considering all PSII subunits and the protonation pattern of all titratable residues. The E(m)(Chla) values were calculated to be 1015-1132 mV for P(D1) and 1141-1201 mV for P(D2), depending on the protonation state of the Mn(4)CaO(5) cluster. The results showed that E(m)(P(D1)) was lower than E(m)(P(D2)), favoring localization of the charge of the cationic state more on P(D1). The P(D1)(?+)/P(D2)(?+) charge ratio determined by the large-scale QM/MM calculations with the explicit PSII protein environment yielded a P(D1)(?+)/P(D2)(?+) ratio of ~80/~20, which was found to be due to the asymmetry in electrostatic characters of several conserved D1/D2 residue pairs that cause the E(m)(P(D1))/E(m)(P(D2)) difference, e.g., D1-Asn181/D2-Arg180, D1-Asn298/D2-Arg294, D1-Asp61/D2-His61, D1-Glu189/D2-Phe188, and D1-Asp170/D2-Phe169. The larger P(D1)(?+) population than P(D2)(?+) appears to be an inevitable fate of the intact PSII that possesses water oxidation activity.     

Contribution of the intramolecular hydrogen bond to the shift of the pKa value and the oxidation potential of phenols and phenolate anions

Intramolecularly OHO[double bond, length as m-dash]C hydrogen bonded phenols, 2-HO-C6H2-3,5-(t-Bu)2-CONH-t-Bu (1-OH), 2-HO-C6H2-5-t-Bu-1,3-(CONH-t-Bu)2 (2-OH) and 2-HO-C6H2-3,5-(t-Bu)2-NHCO-t-Bu (4-OH), were synthesized and their phenolate anions were prepared as tetraethylammonium salts (-1O-(NEt4+), 2-O-(NEt4+) and 4-O-(NEt4+)) with intramolecular NHO(oxyanion) hydrogen bonds. 4-HO-C(6)H(2)-3,5-t-Bu(2)-CONH-t-Bu (3-OH) and its phenolate anion, 3-O-(NEt4+), were synthesized as non-hydrogen bonded references. The presence of intramolecular hydrogen bonds was established through the crystallographic analysis and/or (1)H NMR spectroscopic results. Intramolecular NHO(phenol) hydrogen bonds shift the pK(a) of the phenol to a more acidic value. The results of cyclic voltammetry show that the intramolecular OH...O=C hydrogen bond negatively shifts the oxidation potential of the phenol. In contrast, the intramolecular NHO(oxyanion) hydrogen bond positively shifts the oxidation potential of the phenolate anion, preventing oxidation. These contributions of the hydrogen bond to the pKa value and the oxidation potentials probably play an important role in the formation of a tyrosyl radical in photosystem II.     

Helicates, boxes, and polymers from simple pyridine-alcohol ligands: the impact of the identity of the transition metal ion

The coordination chemistry of 6-methylpyridine-2-methanol (1) and enantiopure (R)-1-(6-methylpyridin-2-yl)ethanol (2) with a range of divalent first-row transition metal salts has been investigated in an effort to determine whether hydrogen-bonded helicates will form, as observed for cobalt(II) salts. Hydrogen-bonded helicates, [Cu2(1)2(1-H)2X2] (X = Cl, Br), were only observed upon combining 1 with CuCl2 and CuBr2 in MeOH solution. Other metal salts led to alternative products, viz. Cu(ClO4)2 in the presence of base gives [Cu2(1)2(1-H)2](ClO4)2, ZnCl2 and ZnBr2 give the 1-D helical coordination polymers [Zn(1-H)Cl]infinity and [Zn(1-H)Br]infinity, a mixture of NiCl2 and Ni(OAc)2 produces the [Ni4(1-H)4Cl2(OAc)2(MeOH)2] cubane, NiCl2 leads to the [Ni4(1-H)4Cl4(MeOH)4] cubane, while MnCl2 gives the known cubane [Mn4(1-H)6Cl4]. The reaction of 2 with CuCl2 produces the mononuclear complex Lambda-[Cu(2)2Cl]Cl, while reaction with CuBr2 leads to a dimer, Lambda,Lambda-[Cu2(2)3(2-H)Br2]Br, which is held together by a single hydrogen bond between the monomeric subunits. The solid-state CD spectra of these latter complexes were recorded and found to be very similar. The temperature-dependent magnetic behavior of [Cu2(1)2(1-H)2X2] (X = Cl, Br), [Cu2(1)2(1-H)2](ClO4)2, [Cu2(2)3(2-H)Br2]Br, and [Ni4(1-H)4Cl2(OAc)2(MeOH)2] was investigated. Weak antiferromagnetic coupling between the copper(II) centers is mediated by the hydrogen bonds in the [Cu2(1)2(1-H)2X2] (X = Cl, Br) complexes.     

Controlling the macrocycle size by the stoichiometry of the applied template ion

Reaction of 4-tert-butyl-2,6-diformylphenol with (1R,2R)- or (1S,2S)-1,2-diaminocyclohexane in the presence of 1 equivalent of Zn(2+) ions leads to selective formation of a chiral 2+2 macrocycle. Application of 0.5 equivalent of Zn(2+) ions under the same conditions leads to selective formation of a chiral 3+3 macrocycle, which forms a cavitand-shaped trinuclear double-decker complex with Zn(II).     

On the Mechanism of the Reaction of alpha-Substituted Ketones with Allyltributylstannane

The mechanisms for the reaction of allyltributylstannane with a number of fragmentation probes, alpha-substituted acetophenones, were studied. All reactions were shown to proceed through free radical chain sequences since they could be initiated by AIBN and inhibited by m-dinitrobenzene (DNB). alpha-Halo- and alpha-(benzoyloxy)acetophenones (I and II, PhCOCR(1)R(2)X; X = F, Cl, Br, OCOPh; R(1), R(2) = H, Me) yielded the allylation products, PhCOCR(1)R(2)CH(2)CH=CH(2)), through a chain sequence involving as the propagation step: an electron transfer from Bu(3)Sn(*) to I and II, fragmentation of the ketyl anion PhCOCR(1)R(2)X(*)(-), and addition of PhCOCR(1)R(2)(*) to allyltributylstannane. The reactions of alpha-(arylsulfonyl)acetophenones (IIIa-c, PhCOCR(1)R(2)Y, Y = SO(2)Tol-p), however, gave a nearly 1:1 mixture of allyl tosyl sulfone and the corresponding ketone, PhCOCHR(1)R(2). The (1)H and (13)C NMR of the reaction mixture between allyltributylstannane and alpha-(p-methylbenzenesulfonyl)isobutyrophenone substantiated the intermediacy of the tin enolate PhC(OSnBu(3))=CMe(2). These results suggested that a radical addition elimination mechanism was involved in the reactions of IIIa-c with allylstannane. The reaction of alpha-phenylthioacetophenone (IV, PhCOCH(2)SPh) gave both the electron transfer and the addition elimination products (PhCOCH(2)CH(2)CH=CH(2), PhCOCH(3)), indicating that both pathways were involved in the formation of the products.     

Dependence of field switched ordered arrays of dinuclear mixed-valence complexes on the distance between the redox centers and the size of the counterions

trans-[(H(2)NCH(2)CH(2)C triple bond N)(dppe)(2)Ru(C triple bond C)(6)Ru(dppe)(2)(N triple bond CCH(2)CH(2)NH(2))][PF(6)](2), 2[PF(6)](2), a derivative of trans-[Cl(dppe)(2)Ru(C triple bond C)(6)Ru(dppe)(2)Cl] functionalized for binding to a silicon substrate, has been prepared and characterized spectroscopically, electrochemically, and with a solid state, single-crystal structure determination. Covalent binding via reaction of one amine group to a boron-doped, smooth Si-Cl substrate is verified by XPS measurements and surface electrochemistry. Vertical orientation is demonstrated by film thickness measurements. Synthesis of the 2[PF(6)](3) mixed-valence complex on the surface is established by electrochemical techniques. Measurement of the ac capacitance of the film at 1 MHz as a function of voltage across the film with a pulse-counter pulse technique demonstrates controlled electric field generation of the two stable mixed-valence forms differing in the spatial location of one electron, that is, switching. As compared to [trans-Ru(dppm)(2)(C triple bond CFc)(NCCH(2)CH(2)NH(2))][PF(6)][Cl], 1[PF(6)][Cl], the magnitude of the capacitance signal per complex observed on switching is shown to increase with increasing distance between the metal centers. Additional experiments on 1[X][Cl] show that the potential for switching 1[X][Cl] increases in the order [X](-) = [SO(3)CF(3)](-) < [PF(6)](-) < [Cl](-). A simple electrostatic model suggests that the smaller is the counterion, the greater is the perturbation of the metal sites and the larger is the barrier for switching.     

助剂前体ZnSO_4浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响

共沉淀法制备了Ru-Zn催化剂,在ZrO_2作分散剂下考察了助剂前体ZnSO_4浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响.并用X-射线衍射(XRD)、X-射线荧光光谱(XRF)、N_2-物理吸附、透射电镜(TEM)和X-射线光电子能谱(XPS)等手段对催化剂进行了表征.结果表明,当ZnSO_4前体浓度低于0.10 mol/L时,Ru-Zn催化剂中Zn以ZnO形式存在,在加氢过程中ZnO可以与反应修饰剂ZnSO_4反应生成(Zn( OH)_2)_3(ZnSO_4)(H_2O)_3盐.继续增加ZnSO_4前体浓度,催化剂中Zn以ZnO和NaZn_4(SO_4)(Cl)(OH)_6·6H_2O盐存在,在加氢过程中ZnO和NaZn_4(SO_4)(Cl)(OH)_6·6H_2O盐可以与反应修饰剂ZnSO_4反应生成(Zn( OH)_2)_3(ZnSO_4)(H_2O)_5.(Zn( OH)_2)_3(ZnSO_4)(H_2O)_x(x=3或5)盐的Zn~(2+)可以转移金属Ru的部分电子.因此,随ZnSO_4前体浓度的增加,(Zn( OH)_2)_3(ZnSO_4)(H_2O)_x的量逐渐增加,金属Ru失电子越多,催化剂活性越低,环己烯选择性越高.0.08 mol/L ZnSO_4前体制备Ru-Zn催化剂给出了59.1%的环己烯收率,而且该催化剂具有良好的重复使用性能和稳定性.     

Nature of the reactants and influence of water on the supramolecular assembly

The influences of the nature of reactants and water on the self-assembly of cationic Cu(II) complex structures containing N-(2-pyridylmethyl)glycine (Hpgly) and N-(2-pyridylmethyl)-l-alanine (Hpala) ligands have been investigated. A metallamacrocycle [Cu(6)(pgly)(3)(spgly)(3)] (ClO(4))(6).9H(2)O has been formed by the reaction of [Cu(pgly)(2)].2H(2)O with Cu(ClO(4))(2).6H(2)O. The hexameric cation has Schiff base and reduced Schiff base ligands alternatively bonded to Cu(II) to provide cyclohexane-like conformation with a cavity diameter of 9.4 A. The reaction of Cu(ClO(4))(2).6H(2)O with Hpgly.HCl yielded [Cu(pgly)(H(2)O)](ClO(4)), which is presumed to have 1D coordination polymeric structure. A [K subset [12-MC-3]] metallacrown, [K(ClO(4))(3)[Cu(3)(pala)(3)]](ClO(4)) has been isolated by reacting Cu(ClO(4))(2) with Kpala in MeCN/MeOH. This [K subset [12-MC-3]] metallacrown further reacts with water to form an infinite 1D coordination polymer [Cu(pala)(H(2)O)(ClO(4))](n)(), which can also be obtained by conducting the reaction in aqueous MeOH.     

Iron-catalyzed olefin epoxidation in the presence of acetic acid: insights into the nature of the metal-based oxidant

The iron complexes [(BPMEN)Fe(OTf)2] (1) and [(TPA)Fe(OTf)2] (2) [BPMEN = N,N'-bis-(2-pyridylmethyl)-N,N'-dimethyl-1,2-ethylenediamine; TPA = tris-(2-pyridylmethyl)amine] catalyze the oxidation of olefins by H2O2 to yield epoxides and cis-diols. The addition of acetic acid inhibits olefin cis-dihydroxylation and enhances epoxidation for both 1 and 2. Reactions carried out at 0 degrees C with 0.5 mol % catalyst and a 1:1.5 olefin/H2O2 ratio in a 1:2 CH3CN/CH3COOH solvent mixture result in nearly quantitative conversions of cyclooctene to epoxide within 1 min. The nature of the active species formed in the presence of acetic acid has been probed at low temperature. For 2, in the absence of substrate, [(TPA)FeIII(OOH)(CH3COOH)]2+ and [(TPA)FeIVO(NCCH3)]2+ intermediates can be observed. However, neither is the active epoxidizing species. In fact, [(TPA)FeIVO(NCCH3)]2+ is shown to form in competition with substrate oxidation. Consequently, it is proposed that epoxidation is mediated by [(TPA)FeV(O)(OOCCH3)]2+, generated from O-O bond heterolysis of the [(TPA)FeIII(OOH)(CH3COOH)]2+ intermediate, which is promoted by the protonation of the terminal oxygen atom of the hydroperoxide by the coordinated carboxylic acid.     

Photoinitiated predissociation of the NO dimer in the region of the second and third NO stretch overtones

Photofragment yield spectra and NO(X(2)Pi(1/2,3/2); v = 1, 2, 3) product vibrational, rotational, and spin-orbit state distributions were measured following NO dimer excitation in the 4000-7400 cm(-1) region in a molecular beam. Photofragment yield spectra were obtained by monitoring NO(X(2)Pi; v = 1, 2, 3) dissociation products via resonance-enhanced multiphoton ionization. New bands that include the symmetric nu(1) and asymmetric nu(5) NO stretch modes were observed and assigned as 3nu(5), 2nu(1) + nu(5), nu(1) + 3nu(5), and 3nu(1) + nu(5). Dissociation occurs primarily via Deltav = -1 processes with vibrational energy confined preferentially to one of the two NO fragments. The vibrationally excited fragments are born with less rotational energy than predicted statistically, and fragments formed via Deltav = -2 processes have a higher rotational temperature than those produced via Deltav = -1 processes. The rotational excitation likely derives from the transformation of low-lying bending and torsional vibrational levels in the dimer into product rotational states. The NO spin-orbit state distribution reveals a slight preference for the ground (2)Pi(1/2) state, and in analogy with previous results, it is suggested that the predominant channel is X(2)Pi(1/2) + X(2)Pi(3/2). It is suggested that the long-range potential in the N-N coordinate is the locus of nonadiabatic transitions to electronic states correlating with excited product spin-orbit states. No evidence of direct excitation to electronic states whose vertical energies lie in the investigated energy region is obtained.     

About the stereoelectronics of the intramolecular addition of allylsilanes to aldehydes

(Z)-omega-Trimethylsilyl-(omega-2)-alken-1-ols are readily accessible by consecutive superbase metalation and silylation of (omega-1)-alken-1-ols. These versatile intermediates may be oxidized to give the corresponding (Z)-omega-trimethylsilyl-(omega-2)-alkenals which, in the presence of trifluoroacetic acid, can be converted into 2-vinylcycloalkanols such as 2-vinylcyclohexanol (2), isopulegol (4), and bis(2-vinylcyclobutyl) ether (8). The stereochemical outcome of these cyclization reactions suggests the interference of a novel electrodynamic effect.