Multi-configuration electron-hole potential method for excited states

The recently proposed electron-hole potential (EHP) method for excited states is extended to the multi-configurational case. The variation equation is solved using the quadratic convergence method. The EHP methods are shown to be approximations to the complete singly excited configuration interaction (CSECI) in the variational sense. Extended Brillouin theorems are proved for the EHP methods. The excitation energies and wave functions obtained by one and two configurational EHP methods agree well with those of the CSECI method. The EHP methods have clear advantage in the computer time requirement over the CI method and are especially suited for a calculation of approximate excited states of large molecules. The EHP methods are applicable to excited states which belong to the same irreducible representation as the ground state.     

Computational study of the aminolysis of esters. The reaction of methylformate with ammonia

The aminolysis of esters is a basic organic reaction considered as a model for the interaction of carbonyl group with nucleophiles. In the present computational study the different possible mechanistic pathways of the reaction are reinvestigated by applying higher level electronic structure theory, examining the general base catalysis by the nucleophile, and a more comprehensive study the solvent effect. Both the ab initio QCISD/6-31(d,p) method and density functional theory at the B3LYP/6-31G(d) level were employed to calculate the reaction pathways for the simplest model aminolysis reaction between methylformate and ammonia. Solvent effects were assessed by the PCM method. The results show that in the case of noncatalyzed aminolysis the addition/elimination stepwise mechanism involving two transition states and the concerted mechanism have very similar activation energies. However, in the case of catalyzed aminolysis by a second ammonia molecule the stepwise mechanism has a distinctly lower activation energy. All transition states in the catalyzed aminolysis are 10-17 kcal/mol lower than those for the uncatalyzed process.     

Meerwein-Ponndorf-Verley alkynylation of aldehydes: essential modification of aluminium alkoxides for rate acceleration and asymmetric synthesis

A novel carbonyl alkynylation has been accomplished based on utilization of the Meerwein-Ponndorf-Verley (MPV) reaction system. The success of the MPV alkynylation crucially depends on the discovery of the remarkable ligand acceleration effect of 2,2'-biphenol. For example, the alkynylation of chloral (2c) with the aluminium alkoxide 6(R = Ph), prepared in situ from Me(3)Al, 2,2'-biphenol and 2-methyl-4-phenyl-3-butyn-2-ol (1a) as an alkynyl source, proceeded smoothly in CH(2)Cl(2) at room temperature to give the desired propargyl alcohol 3ca in almost quantitative yield after 5 h stirring. The characteristic feature of this new transformation involving no metal alkynides can be visualized by the fact that the alkynyl group bearing keto carbonyl was transferred successfully to aldehyde carbonyl without any side reactions on keto carbonyl. Although the use of (S)-1,1[prime or minute]-bi-2-naphthol and its simple analogues was found to be unsuitable for inducing asymmetry in this reaction, design of new chiral biphenols bearing a certain flexibility of the biphenyl axis led to satisfactory results in terms of enantioselectivity as well as reactivity.     

Can chlorine anion catalyze the reaction of HOCl with HCl?

The reaction of HOCl + HCl → Cl₂ + H₂O in the presence of chlorine anion Cl⁻ has been studied using ab initio methods. The overall exothermicity is 15.5 kcal mol⁻¹ and this reaction has been shown to have a high activation barrier of 46.5 kcal mol⁻¹. Cl⁻ is found to catalyze the reaction via the formation of HOCl·Cl⁻, ClH·HOCl·Cl⁻ and Cl⁻·H₂) intermediate ion-molecule complexes or by interacting with a concerted four-center transition state of the reaction of HOCl + HCl.     

Regulation of geometry around the ruthenium center of bis(2-pyridinecarboxylato) complexes by the nitrosyl moiety: syntheses, structures, and theoretical studies

cis-[Ru(NO)Cl(pyca)(2)] (pyca = 2-pyridinecarboxylato), in which the two pyridyl nitrogen atoms of the two pyca ligands coordinate at the trans position to each other and the two carboxylic oxygen atoms at the trans position to the nitrosyl ligand and the chloro ligand, respectively (type I shown as in Chart 1), reacted with NaOCH(3) to generate cis-[Ru(NO)(OCH(3))(pyca)(2)] (type I). The geometry of this complex was confirmed to be the same as the starting complex by X-ray crystallography: C(13.5)H(13)N(3)O(6.5)Ru; monoclinic, P2(1)/n; a = 8.120(1), b = 16.650(1), c = 11.510(1) A; beta = 99.07(1) degrees; V = 1536.7(2) A(3); Z = 4. The cis-trans geometrical change reaction occurred in the reactions of cis-[Ru(NO)(OCH(3))(pyca)(2)] (type I) in water and alcohol (ROH, R = CH(3), C(2)H(5)) to form [[trans-Ru(NO)(pyca)(2)](2)(H(3)O(2))](+) (type V) and trans-[Ru(NO)(OR)(pyca)(2)] (type V). The reactions of the trans-form complexes, trans-[Ru(NO)(H(2)O)(pyca)(2)](+) (type V) and trans-[Ru(NO)(OCH(3))(pyca)(2)] (type V), with Cl(-) in hydrochloric acid solution afforded the cis-form complex, cis-[Ru(NO)Cl(pyca)(2)] (type I). The favorable geometry of [Ru(NO)X(pyca)(2)](n)(+) depended on the nature of the coexisting ligand X. This conclusion was confirmed by theoretical, synthetic, and structural studies. The mono-pyca-containing nitrosylruthenium complex (C(2)H(5))(4)N[Ru(NO)Cl(3)(pyca)] was synthesized by the reaction of [Ru(NO)Cl(5)](2)(-) with Hpyca and characterized by X-ray structural analysis: C(14)H(24)N(3)O(3)Cl(3)Ru; triclinic, Ponemacr;, a = 7.631(1), b = 9.669(1), c = 13.627(1) A; alpha = 83.05(2), beta = 82.23(1), gamma = 81.94(1) degrees; V = 981.1(1) A(3); Z = 2. The type II complex of cis-[Ru(NO)Cl(pyca)(2)] was synthesized by the reaction of [Ru(NO)Cl(3)(pyca)](-) or [Ru(NO)Cl(5)](2)(-) with Hpyca and isolated by column chromatography. The structure was determined by X-ray structural analysis: C(12)H(8)N(3)O(5)ClRu; monoclinic, P2(1)/n; a = 10.010(1), b = 13.280(1), c = 11.335(1) A; beta = 113.45(1) degrees; V = 1382.4(2) A(3); Z = 4.     

Development of miniaturized multi-channel high-performance liquid chromatography for high-throughput analysis

We have developed miniaturized multi-channel high-performance liquid chromatography (HPLC) system. With this system, we can simultaneously separate multiple samples, using a single high-pressure gradient pump, a chip-based sample injection unit, a monolithic silica capillary column array, and a multi-channel UV detection unit based on fiber optics. The injection unit has a simplified structure composed of brass housing and a quartz microchip having microchannels and access ports, which enable a direct injection of sample to multi-channel by commercial multichannel micropipette. Moreover, that possesses a function of microvalve, and on-chip definition of sample injection plugs achieved with a cross channel injection method, providing each column of monolithic silica capillary array. The substances in channels were simultaneously detected with UV having multiple cells. Standard samples were analyzed for characterizing newly developed system, and sharp peaks were obtained with reproducibility data of < 0.9% (R.S.D.). Analysis of tryptic digestion of casein was also employed. These results show that the novel multi-channel HPLC system has the benefits for the high-throughput analysis in the post-genomic analysis/combinatorial chemistry.