Silicon hydrides and nickel complexes : III. Hydrosilylation of olefins with dichloro[1,2-bis-(dimethylphosphino)-1,2-dicarba-closo-dodecaborane]-nickel(II) as catalyst

The hydrosilylation of olefins catalyzed by nickel(II) chloride complexed with 1,2-bis(dimethylphosphino)-1,2-dicarba-closo-dodecaborane produces terminal and internal adducts in comparable amounts. This unusual feature of the reaction is explained in terms of the electron-accepting nature of the carboranyl group.     

Energy funneling of IR photons captured by dendritic antennae and acceptor mode specificity: anti-stokes resonance raman studies on iron(III) porphyrin complexes with a poly(aryl ether) dendrimer framework

A series of poly(aryl ether) dendrimer chloroiron(III) porphyrin complexes (LnTPP)Fe(III)Cl (number of aryl layers [n]=3 to 5) were synthesized, and their Boltzmann temperatures under IR irradiation were evaluated from ratios of Stokes to anti-Stokes intensities of resonance Raman bands. While the Boltzmann temperature of neat solvent was unaltered by IR irradiation (LnTPP)Fe(III)Cl (n=3 to 5), all showed a temperature rise that was larger than that of the solvent and greater as the dendrimer framework was larger. Among vibrational modes of the metalloporphyrin core, the temperature rise of an axial Fe-Cl stretching mode at 355 cm-1 was larger than that for a porphyrin in-plane mode at 390 cm-1. Although most of the IR energy is captured by the phenyl nu8 mode at 1597 cm-1 of the dendrimer framework, an anti-Stokes Raman band of the phenyl nu8 mode was not detected, suggesting the extremely fast vibrational relaxation of the phenyl mode. From these observations, it is proposed that the energy of IR photons captured by the aryl dendrimer framework is transferred to the axial Fe-Cl bond of the iron porphyrin core and then relaxed to the porphyrin macrocycle.     

Homogeneous palladium catalyst suppressing Pd black formation in air oxidation of alcohols

In homogeneous catalyst systems, there is the persistent problem that metal aggregation and precipitation cause catalyst decomposition and considerable loss of catalytic activity. Pd black formation is a typical example. Pd catalysts are known to easily aggregate and form Pd black, although they realize a wide variety of useful reactions in organic synthesis. In order to overcome this intrinsic problem of homogeneous Pd catalysis, we explored a new class of Pd catalyst by adopting aerobic oxidation of alcohols as a probe reaction. Herein we report a new catalyst system that suppresses the Pd black formation even under air and with a high substrate to catalyst molar ratio (S/C: more than 1000) in oxidation of alcohols. The novel pyridine derivatives having a 2,3,4,5-tetraphenylphenyl substituent and its higher dendritic unit at the 3-position of the pyridine ring were found to be excellent ligands with Pd(OAc)2 in the palladium-catalyzed air (balloon) oxidation of alcohols in toluene at 80 degrees C. Comparison with structurally related pyridine ligands revealed that introduction of the 2,3,4,5-tetraphenylphenyl substituent at the 3-position of pyridine ring effectively suppresses the Pd black formation, maintaining the catalytic activity for a long time to give aldehydes or ketones as products in high yields.     

Molecular Recognition of Nucleic Acid Bases in Water by Hydrogen Bonding of Poly(vinyldiaminotriazine)

Poly(2-vinyl-4,6-diamino-1,3,5-triazine) efficiently binds nucleic acid bases and nucleosides in water by using complementary hydrogen bonding. The binding activity decreases in the order: U, T > A C, G. The corresponding monomer shows virtually no activity, indicating a predominant role of polymer effect for the molecular recognition in water.     

Aerobic oxidation of methyl p-tolyl sulfide catalyzed by a remarkably labile heteroscorpionate RuII-aqua complex,fac-[RuII(H2O)(dpp)(tppm)]2+

fac-[RuII(Cl)(dpp)(L3)]+ (L3 = tris(pyrid-2-yl)methoxymethane (tpmm) = [1A]+ and tris(pyrid-2-yl)pentoxymethane (tppm) = [1B]+ and dpp = di(pyrazol-1-yl)propane) rapidly undergo ligand substitution with water to form fac-[RuII(H2O)(dpp)(L3)]2+ (L3 = tpmm = [2A]2+ and tppm = [2B]2+). In the structure of [2A]2+, the distorted octahedral arrangement of ligands around Ru is evident by a long Ru(1)-O(40) of 2.172(3) A and a large angle O(40)-Ru(1)-N(51) of 96.95(14) degrees . The remarkably short distance between O(40) of H2O and H(45a) of dpp confirms the heteroscorpionate ligand effect of dpp on H2O. [2B]2+ aerobically catalyzes methyl p-tolyl sulfide to methyl p-tolyl sulfoxide in 1,2-dichlorobenzene at 25.0 +/- 0.1 degrees C under 11.4 psi of O2. Experimental facts in support of this aerobic sulfide oxidation are the absence of H2O2 and the oxidative reactivity of the putative Ru(IV)-oxo intermediate toward methyl p-tolyl sulfide, 2-propanol, and allyl alcohol. This study provides the first documented example of aerobic-sulfide oxidation catalyzed by the remarkably labile heteroscorpionate Ru(II)-aqua complex without the formation of a highly reactive peroxide as an intermediate.     

Preparation of a novel molecularly imprinted polymer using a water-soluble crosslinking agent

A molecularly imprinted polymer was prepared using a water-soluble crosslinking agent. An ionic complex was utilized as the assembly for the template molecule and the functional monomer, and water as porogenic solvent during preparation of the imprinted polymer. The results of chromatographic evaluations for the prepared polymer suggested that the polymer had much lower hydrophobicity compared with usual octadecyl group bonded silica or the usual molecular imprinted polymer prepared from ethyleneglycol dimethacrylate, and the selective recognition ability for template molecule in the completely aqueous condition.     

New reactions of 1-alkynes catalyzed by transition metal complexes

Recently discovered catalytic reactions with ruthenium and lanthanide metal complexes have extended the scope of 1-alkynes as useful reagents. The specific formation of aryl-substituted (Z)-1,3-enzymes via the dimerization of HC(triple bond) CR(1) (R(1) = aryl) has been attained using dimeric lanthanide complexes, the catalytic activity of which appears to be unaffected by time. The dimerization of HC(triple bond) CR(2) (R(2) = t-Bu, SiMe(3)) catalyzed by Ru(cod)(cot)/PR(3) or RuH(2)(PPh(3))(3) produces a good yield of butatrienes (Z)R(2)CH=C=C=CHR(2) with a high degree of selectivity. Under certain conditions, HC(triple bond) C=SiMe(3) dimerizes to yield exclusively (Z)-M(3)Si-C(triple bond) C-CH=CH-SiMe(3). The hydration of HC(triple bond)CR(3) (R(3) = alkyl, aryl) catalyzed by RuCl(2)/PR'(3) or CpRuCl(PR"(3))(2) has realized the first example of anti-Markovnikov regioselectivity in an addition reaction of water that produces aldehydes R(3)CH(2)bond;CHO. The application of this reaction to propargylic alcohols has lead to their formal isomerization to alpha,beta-unsaturated aldehydes. In contrast, the addition of amines R(4)bond;NH(2) (R(4) = aryl) to HCtbond;CR(5) (R(5) = alkyl, aryl) conforms to Markovnikov's rule to produce ketimines R(5)bond;(C=NR(4))bond;CH(3) when catalyzed by a Ru(3)(CO)(12)/additive. Since the reaction can be performed in air without the need for any solvents, it enables the practical synthesis of aromatic ketimines, which are difficult to prepare by conventional methods. The synthesis of indoles using deactivated anilines is one practical application of this reaction. The mechanisms of some of these reactions have been analyzed in detail with the aid of theoretical calculations.     

Femtosecond absorption study of photodissociation of diphenylcyclopropenone in solution: reaction dynamics and coherent nuclear motion

Reaction dynamics and coherent nuclear motions in the photodissociation of diphenylcyclopropenone (DPCP) were studied in solution by time-resolved absorption spectroscopy. Subpicosecond transient absorption spectra were measured in the visible region with excitation at the second absorption band of DPCP. The obtained spectra showed a new short-lived band around 480 nm immediately after photoexcitation, which is assignable to the initially populated S(2) state of DPCP before the dissociation. The dissociation takes place from this excited state (the precursor of the reaction) with a time constant of 0.2 ps, and the excited state of diphenylacetylene (DPA) is generated as the reaction product. The transient absorption after the dissociation decayed with a time constant of 8 ps that is very close to the S(2)-state lifetime of DPA, but the spectrum of this 8-ps component was different from the S(2) absorption observed with direct photoexcitation of DPA. We conclude that the dissociation of DPCP generates the S(2) state of DPA that probably has a cis-bent structure. At later delay times (>30 ps), the transient absorption signals are very similar to those obtained by direct photoexcitation of DPA. This confirmed that the electronic relaxation from the S(2) state of the product DPA occurs in a similar manner to that of DPA itself, i.e., the internal conversion to the S(1) state and subsequent intersystem crossing to the T(1) state. In order to examine the coherent nuclear dynamics in this dissociation reaction, we carried out time-resolved absorption measurements for the 480-nm band with 70 fs resolution. It was found that an underdamped oscillatory modulation with a 0.1-ps period is superposed on the decay of the precursor absorption. This indicates that DPCP exhibits a coherent nuclear motion having a approximately 330-cm(-1) frequency in the dissociative excited state. Based on a comparison with the measured and calculated Raman spectra of ground-state DPCP, we discuss the assignment of the "330-cm(-1) vibration" and attribute it to a vibration involving the displacement of the CO group as well as the deformation of the Ph-C[Double Bond]C-Ph skeleton. We consider that this motion is closely related to the reaction coordinate of the photodissociation of DPCP.     

Cobaltporphyrin‐adsorbed carbon black: highly efficient electrocatalysts for oxygen reduction

meso‐Substituted cobalt porphyrins adsorbed on carbon black were prepared as catalysts for the electroreduction of O₂. The catalyst, which was prepared by using a homogenizer in mixing cobalt tetraethylporphyrin and carbon black, gave rise to electroreduction of O₂ at a remarkably positive potential (E_p = 0.45 V versus saturated calomel electrode (SCE)) and showed a high selectively for the four‐electron reduction (n = 3.8). Electrochemical study and extended X‐ray absorption fine structure (EXAFS) analysis revealed that the adsorbed face‐to‐face dimeric aggregates of cobalt porphyrin molecules were highly efficient catalysts for electroreduction of O₂. Copyright © 2005 John Wiley & Sons, Ltd.     

Polymers having stable radicals. II. Synthesis of nitroxyl polymers from 4-methacryloyl derivatives of 1-hydroxy-2,2,6,6-tetramethylpiperidine

Polymers having stable pendant . radicals were synthesized through their precursor polymers by oxidizing them in air or by H₂O₂–Na₂WO₄. Hydrochlorides and sulfates of 4-methacryloylamino- and 4-methacryloyloxy-1-hydroxy-2,2,6,6-tetramethylpiperidines were synthesized as precursor monomers and polymerized by using α,α′-azobisisobutyronitrile under appropriate conditions to precursor polymers of high molecular weight: poly-4-methacryloylamino-/oxy-1-hydroxy-2,2,6,6-tetramethylpiperidinehydrochlorides and sulfates. The precursor polymers were converted to polymers having nitroxyl stable radicals, i.e., poly-4-methacryloylamino-/oxy-2,2,6,6-tetramethylpiperidine-1-oxyls, by oxidation in air or with H₂O₂–Na₂WO₄ without any main-chain scission. The structure of the resultant stable radical polymers was determined by infrared, ultraviolet, and ESR spectroscopy. Based on the results of spectroscopic analysis and Kjeldahl analysis, the transformation from precursors to nitroxyl stable radical polymers was found to be quantitative. Investigations on the applicability of polymeric nitroxyl radicals to oxidation-reduction reactions were attempted by means of polarography; the reduction half-wave potential was found to be ?1.16 V for the mercury pool.