Showing papers in "Chemistry: A European Journal in 2002"

Size‐Dependent Chemistry: Properties of Nanocrystals

Abstract: Properties of materials determined by their size are indeed fascinating and form the basis of the emerging area of nanoscience. In this article, we examine the size dependent electronic structure and properties of nanocrystals of semiconductors and metals to illustrate this aspect. We then discuss the chemical reactivity of metal nanocrystals which is strongly dependent on the size not only because of the large surface area but also a result of the significantly different electronic structure of the small nanocrystals. Nanoscale catalysis of gold exemplifies this feature. Size also plays a role in the assembly of nanocrystals into crystalline arrays. While we owe the beginnings of size-dependent chemistry to the early studies of colloids, recent findings have added a new dimension to the subject.

Preparation and characterization of new room temperature ionic liquids.

Abstract: A new series [CnOm mim][X] of imidazolium cation-based room temperature ionic liquids (RTILs), with ether and alcohol functional groups on the alkyl side-chain has been prepared. Some physical properties of these RTILs were measured, namely solubility in common solvents, viscosity and density. The solubility of LiCl, HgCl2 and LaCl3 in room temperature ionic liquids was also determined. The features of the solid–liquid phase transition were analysed, namely the glass transition temperature and the heat capacity jump associated with the transition from the non-equilibrium glass to the metastable supercooled liquid. These properties were compared with those reported for the 1-n-alkyl-3-methylimidazolium [Cn mim][X] series. While the density and solid–liquid phase transition properties are similar for both series, the new RTILs present a considerably lower viscosity and an increased ability to dissolve HgCl2 and LaCl3 (up to 16 times higher).

Double‐Stranded Helices and Molecular Zippers Assembled from Single‐Stranded Coordination Polymers Directed by Supramolecular Interactions

Abstract: Using three nonlinear dicarboxylates, isophthalate (ipa), 4,4'-oxybis(benzoate) (oba), and ethylenedi(4-oxybenzoate) (eoba), we have prepared five neutral infinite copper(II) dicarboxylate coordination polymers containing lateral aromatic chelate ligands, namely [Cu(ipa)(2,2'-bpy)]n.2nH2O (1), [Cu2(ipa)2(phen)2H2O]n (2), [Cu(oba)(phen)]n (3), [Cu(oba)(2,2'-bpy)]n (4), and [Cu(eoba)(phen)]n (5; 2,2'-bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) by hydrothermal synthesis. X-ray single-crystal structural analyses of these complexes reveal that the nonlinear flexible or V-shaped dicarboxylates can induce the helicity or flexuousity of the polymeric chains and aromatic chelate ligands are important in providing potential supramolecular recognition sites for pi-pi aromatic stacking interactions. An appropriate combination of the bridging dicarboxylate and aromatic chelate can induce a pair of single-stranded helical or flexuous chains to generate a double-stranded helix or molecular zipper through supramolecular interactions, respectively.

Inorganic Semiconductor Nanowires: Rational Growth, Assembly, and Novel Properties

Abstract: Rationally controlled growth of inorganic semiconductor nanowires is important for their applica- tions in nanoscale electronics and photonics. In this article, we discuss the rational growth, physical proper- ties, and integration of nanowires based on the results from the authors× laboratory. The composition, diameter, growth position, and orientation of the nanowires are controlled based on the vapor ± solid ± liquid (VLS) crystal growth mechanism. The thermal stability and optical properties of these semiconductor nanowires are investigated. Particularly, ZnO nanowires with well- defined end surfaces can function as room-temperature ultraviolet nanolasers. In addition, a novel microfluidic- assisted nanowire integration (MANI) process was de- veloped for the hierarchical assembly of nanowire build- ing blocks into functional devices and systems.

Novel flexible frameworks of porous cobalt(II) coordination polymers that show selective guest adsorption based on the switching of hydrogen-bond pairs of amide groups

Abstract: Four porous crystalline coordination polymers with two-dimensional frameworks of a double-edged axe-shaped motif, [[Co(NCS)(2)(3-pia)(2)] x 2 EtOH.11 H(2)O](n) (1 a), [[Co(NCS)(2)(3-pia)(2)] x 4 Me(2)CO](n) (3 a), [[Co(NCS)(2)(3-pia)(2)] x 4T HF](n) (3 b) and [[Co(NCS)(2)(3-pna)(2)](n)] (5), have been synthesized by the reaction of cobalt(II) thiocyanate with N-(3-pyridyl)isonicotinamide (3-pia) or N-(3-pyridyl)nicotinamide (3-pna). X-ray crystallographic characterization reveals that adjacent layers are stacked such that channels are created, except in 5. The channels form a hydrogen-bonded interior for guest molecules; in practice, 1 a contains ethanol and water molecules as guests in the channels with hydrogen bonds, whereas 3 b (3 a) contains tetrahydrofuran (acetone) molecules. In 1 a, the "double-edged axe-shaped" motifs in adjacent sheets are not located over the top of each other, while the motifs in 3 b stack so perfectly as to overlap each other in an edge-to-edge fashion. This subtle change in the three-dimensional framework is associated with the template effect of the guests. Compound 5 has no guest molecules and, therefore, the amide groups in one sheet are used for hydrogen-bonding links with adjacent sheets. Removal of the guest molecules from 1 a and 3 b (3 a) causes a structural conversion accompanied by a color change. Pink 1 a cannot retain its original framework and changes into a blue amorphous compound. On the other hand, the framework of pink 3 b (3 a) is transformed to a new crystalline framework of violet 4. Interestingly, 4 reverts to the original pink crystals of 3 b (3 a) when it is exposed to THF (or acetone) vapor. Spectroscopic measurements (visible, EPR, and IR) provide a clue to the crystal-to-crystal transformation; on removal of the guests, the amide groups are used to form the beta sheet-type hydrogen bonding between the sheets, and thus the framework withstands significant stress on removal of guest molecules. This mechanism is attributed to the arrangement of the adjacent sheets so suited in regularity that the beta sheet-type structure forms efficiently. The apohost 4 does not adsorb cyclopentane, showing a guest selectivity that, in addition to size, hydrogen-bonding capability is required for the guest molecules. The obtained compound is categorized as a member of a new generation of compounds tending towards functional porous coordination polymers.

Highly Active Palladium/Activated Carbon Catalysts for Heck Reactions: Correlation of Activity, Catalyst Properties, and Pd Leaching

Abstract: A variety of palladium on activated carbon catalysts differing in Pd dispersion, Pd distribution, Pd oxi- dation state, and water content were tested in Heck reactions of aryl bro- mides with olefins. The optimization of the catalyst (structure ± activity relation- ship) and reaction conditions (temper- ature, solvent, base, and Pd loading) allowed Pd/C catalysts with very high activity for Heck reactions of unactivat- ed bromobenzene (turnover number (TON) 18 000, turnover frequency (TOF) up to 9000, Pd concentrations down to 0.005 mol %) to be developed. High Pd dispersion, low degree of re- duction, sufficient content of water, and uniform Pd impregnation are criteria for the most active system. The catalysts combine high activity and selectivity under ambient conditions (air and mois- ture), easy separation (filtration), and quantitative recovery of palladium. De- termination of Pd in solution after and during the reaction, and catalyst charac- terization before and after the reaction (transmission electron microscopy (TEM), X-ray diffraction (XRD)), indi- cate dissolution/reprecipitation of palla- dium during the reaction. The Pd con- centration in solution is highest at the beginning of the reaction and is a mini- mum ( 1 ppm) at the end of the reac- tion. Palladium leaching correlates sig- nificantly with the reaction parameters.

Synthesis of a giant 222 carbon graphite sheet.

Abstract: In this paper we present the synthesis and characterization of the so far largest polycyclic aromatic hydrocarbon (PAH), containing 222 carbon atoms or 37 separate benzene units. First a suitable three-dimensional oligophenylene precursor molecule is built up by a sequence of Diels-Alder and cyclotrimerization reactions and then planarized in the final step by oxidative cyclodehydrogenation to the corresponding hexagonal PAH. Structural proof is based on isotopically resolved MALDI-TOF mass spectra and electronic characteristics are studied by UV/Vis spectroscopy.

Nanowires as building blocks for self-assembling logic and memory circuits.

Abstract: The concept of assembling electronic circuits from metal nanowires is discussed. These nanowires are synthesised electrochemically by using porous membranes as templates. High aspect ratio wires, which range from 15 to 350 nm in diameter and contain "stripes" of different metals, semiconductors, colloid/polymer multilayers, and self-assembling monolayers have been made by this technique. By using the distinct surface chemistry of different stripes, the nanowires can be selectively derivatized and positioned on patterned surfaces. This allows the current-voltage properties of single and crossed nanowire devices to be measured. Nanowire conductors, rectifiers, switches, and photoconductors have been characterized. Techniques are still being developed for assembling sublithographic scale nanowires into cross-point arrays for memory and logic applications.

Surface oxidation of carbon nanofibres

Abstract: Carbon nanofibres of the fishbone and parallel types were surface-oxidised by several methods. The untreated and oxidised fibres were studied with infrared spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy (XPS). Oxidation in a mixture of concentrated nitric and sulfuric acids proved to be the most effective method for creating oxygen-containing surface groups. This treatment results not only in the formation of carboxy and carboxyic anhydride groups, but also in the generation of ether-type oxygen groups between graphitic layers that are puckered at their edges. The IR spectroscopic data clearly show that the formation of oxygen-containing surface groups occurs at defect sites on the carbon nanofibres and that oxidation proceeds via carbonyl groups and other oxides to carboxy and carboxyic anhydride groups. Owing to the presence of defects, the two types of fibre have similar surface reactivities. With parallel nanofibres, in contrast to fishbone fibres, the macroscopic structure was severely affected by treatment with HNO(3)/H(2)SO(4). The HNO(3)/H(2)SO(4)-treated fibres are highly wettable by water.

Supramolecular Polymers Generated from Heterocomplementary Monomers Linked through Multiple Hydrogen-Bonding Arrays—Formation, Characterization, and Properties

Abstract: Supramolecular polymers are described that are derived from the association of two homoditopic heterocomplementary monomers through sextuple hydrogen-bonding arrays. They form fibers and a variety of different materials depending on the conditions. The strong affinity of the DAD-DAD (D=donor, A=acceptor) hydrogen-bonding sites for double-faced cyanuric acid type wedges drives the supramolecular polymeric assembly in apolar and chlorinated organic solvents. The marked influence of stoichiometry, as well as end-capping and cross-linking agents upon fiber formation is revealed in solution and by electron microscopy (EM). The results further contribute to the development of a supramolecular polymer chemistry that comprises reversible polymers formed through recognition-controlled noncovalent connections between the molecular components. Such materials are, by nature, dynamic and present adaptive character in view of their ability to respond to external stimuli.

Core-substituted naphthalene bisimides: new fluorophors with tunable emission wavelength for FRET studies.

Abstract: Highly colored and photoluminescent naphthalene bisimide dyes have been synthesized from 2,6-dichloronaphthalene bisanhydride 1 by means of a stepwise nucleophilic displacement of the two chlorine atoms by alkoxides and/or alkyl amines. The alkoxy-substituted derivatives are yellow dyes with green emission and low photoluminescence quantum yields, whereas the amine-substituted derivatives exhibit a color range from red to blue with strong photoluminescence up to 76%. Structure-property relationships for this class of two-dimensional chromophores were evaluated based on a single-crystal X-ray analysis for dye 5a, the observed solvatochromism, and quantum-chemical calculations. Owing to the simple tuning of the absorption properties over the whole visible range by the respective substituents, the pronounced brilliancy, and the intense photoluminescence, this class of dyes is considered to be highly suited for numerous applications such as fluorescent labeling of biomacromolecules and light-harvesting in supramolecular assemblies. As an important step towards such applications efficient FRET (fluorescence resonance energy transfer) has been demonstrated for a covalently tethered bichromophoric compound that contains a red and a blue naphthalene bisimide dye.

Selective and Shape-Selective Baeyer–Villiger Oxidations of Aromatic Aldehydes and Cyclic Ketones with Sn-Beta Zeolites and H2O2

Abstract: Sn-Beta is used as a heterogeneous catalyst for the Baeyer-Villiger reaction with hydrogen peroxide. Cyclic ketones are transformed into the corresponding lactones, while unsaturated ketones are oxidized to the corresponding unsaturated lactones with very high chemoselectivity. The catalyst is also selective for the oxidation of aromatic aldehydes with H2O2, producing the formate ester or the corresponding hydrolyzed product, that is the alcohol. Shape-selective oxidations are observed for isomeric reactants with different molecular shapes. The catalytic Sn sites have been characterized by 119Sn MAS-NMR spectroscopy, and tetrahedral incorporation into the zeolite framework has been demonstrated. In situ IR spectroscopy and 18O labeling experiments have shown that the oxidation mechanism involves an intermediate of the Criegee type.

Synthesis, Structure and Magnetism of Homologous Series of Polycrystalline Cobalt Alkane Mono- and Dicarboxylate Soaps

Abstract: Carboxylate-bridged chain complexes of CoII (the diaquacobalt(II) mono- and α,ω-dialkanoates) form two homologous series of layered compounds which have been fully characterised both structurally and magnetically. The crystal structures of two selected members, [Co{CH3(CH2)10COO}2(H2O)2] and [Co{CH3(CH2)18COO}2(H2O)2], have been solved by X-ray powder diffraction and selected-area electron diffraction methods, and refined by the Rietveld technique. Crystal data: monoclinic, P 21/a; a=9.688(1), b=7.5495(9), c=37.281(5) A, β=96.70(3)°, Z=4; and monoclinic, P 21/a; a=9.7260(7), b=7.5477(7), c=57.53(1) A, β=94.66(4)°, Z=4, respectively. Their isomorphous structures contain layers of octahedral diaquacobalt(II) ions bonded to two chemically inequivalent alkanoates, one chelating and one bridging two Co atoms about 6.3 A apart, thus confirming the rare anti–anti conformation mode of the μ-RCOO groups recently proposed for diaquacobalt(II) α,ω-dodecanedioate. Extensive magnetic characterisation allowed estimation of the feeble antiferromagnetic coupling, which is weaker in the mono- than in the dialkanoate series.

Octahedral bipyridine and bipyrimidine dioxomolybdenum(VI) complexes: characterization, application in catalytic epoxidation, and density functional mechanistic study.

Abstract: Complexes of the general formula [MoO 2 X 2 L 2 ] (X=Cl, Br, Me; L 2 =bipy, bpym) have been prepared and fully characterized, including X-ray crystallographic investigations of all six compounds. Additionally, the highly soluble complex [MoO 2 Cl 2 (4,4'-bis(hexyl)-2,2'-bipyridine)] has been synthesized. The reaction of the complexes with tert-butyl hydroperoxide (TBHP) is an equilibrium reaction, and leads to Mo V I η 1 -alkylperoxo complexes that selectively catalyze the epoxidation of olefins. Neither the Mo-X bonds nor the Mo-N bonds are cleaved during this reaction. These experimental results are supported by theoretical calculations, which show that the attack of TBHP at the Mo center through the X-O-N face is energetically favored and the TBHP hydrogen atom is transferred to a terminal oxygen of the Mo=O moiety. After the attack of the olefin on the Mo-bound peroxo oxygen atom, epoxide and tert-butyl alcohol are formed. The latter compound acts as a competitive inhibitor for the TBHP attack, and leads to a significant reduction in the catalytic activity with increasing reaction time.

End-cap stabilized oligoynes: model compounds for the linear sp carbon allotrope carbyne.

Abstract: Three series of differently 3,5-disubstituted alpha,omega-diphenylpolyynes Ar-(C[triple bond]C)n-Ar (n=2, 4, 6, 8, 10) were synthesized under optimized Cadiot-Chodkiewicz conditions, isolated and completely characterized. These compounds can be considered as model substances for the hypothetical one-dimensional carbon allotrope carbyne Cx. The longest sp-carbon chain contains 20 atoms and is therefore the longest, purely organic polyyne studied with NMR techniques. Extinction coefficients over 600,000 M(-1) cm(-1) represent the highest measured quantitative values for that compound class so far. Comparisons with previous investigations and electrochemical studies allow the assignment of absorption for both wavelength regions structuring the UV/Vis spectra. Based on the trends in the spectroscopic behaviour of those molecules with increasing chain length, electronic as well as the NMR properties of carbyne are predicted, in line with our previously reported results. The observed stability properties promise the synthesis of even longer polyynes.

Design of Coordination Polymer Gels as Stable Catalytic Systems

Abstract: Here we report the first example of catalytic metallogels, which are formed irreversibly in dimethylsulfoxide via the creation of cross-linked, three-dimensional coordination polymer networks by using transition-metal ions with multiple sites available for coordination and multidentate ligands. Conformational flexibility of the ligands and slow formation of the coordination polymers apparently favor the gelation. These metallogels are stable in water and most organic solvents and can catalyze the oxidation of benzyl alcohol to benzaldehyde by using their PdII moieties as the catalytic centers. The best catalytic turnover of the metallogel is twice that of [Pd(OAc)2] under similar reaction conditions.

Structure validation of natural products by quantum-mechanical GIAO calculations of 13C NMR chemical shifts.

Abstract: Geometry optimization and GIAO (gauge including atomic orbitals) 1 3 C NMR chemical shift calculations at Hartree-Fock level, using the 6-31G(d) basis set, are proposed as a tool to be applied in the structural characterization of new organic compounds, thus providing useful support in the interpretation of experimental NMR data. Parameters related to linear correlation plots of computed versus experimental 1 3 C NMR chemical shifts for fourteen low-polar natural products, containing 10-20 carbon atoms, were employed to assess the reliability of the proposed structures. A comparison with the hybrid B3LYP method was carried out to evaluate electron correlation contributions to the calculation of 1 3 C NMR chemical shifts and, eventually, to extend the applicability of such computational methods to the interpretation of NMR spectra in apolar solutions. The method was tested by studying three examples of revised structure assignments, analyzing how the theoretical 1 3 C chemical shifts of both correct and incorrect structures matched the experimental data.

Simultaneously multiply-configurable or superposed molecular logic systems composed of ICT (Internal Charge Transfer) chromophores and fluorophores Integrated with one- or two-ion receptors

Abstract: Integrated "ICT chromophore-receptor" systems show ion-induced shifts in their electronic absorption spectra. The wavelength of observation can be used to reversibly configure the system to any of the four logic operations permissible with a single input (YES, NOT, PASS 1, PASS 0), under conditions of ion input and transmittance output. We demonstrate these with dyes integrated into Tsien's calcium receptor, 1-2. Applying multiple ion inputs to 1-2 also allows us to perform two- or three-input OR or NOR operations. The weak fluorescence output of 1 also shows YES or NOT logic depending on how it is configured by excitation and emission wavelengths. Integrated "receptor(1)-ICT chromophore-receptor(2)" systems 3-5 selectively target two ions into the receptor terminals. The ion-induced transmittance output of 3-5 can also be configured via wavelength to illustrate several logic types including, most importantly, XOR. The opposite effects of the two ions on the energy of the chromophore excited state is responsible for this behaviour. INHIBIT and REVERSE IMPLICATION are two of the other logic types seen here. Integration of XOR logic with a preceding OR operation can be arranged by using three ion inputs. The fluorescence output of these systems can be configured via wavelength to display INHIBIT or NOR logic under two-input conditions. The superposition or multiplicity of logic gate configurations is an unusual consequence of the ability to simultaneously observe multiple wavelengths.

Tuning the activity of catechol oxidase model complexes by geometric changes of the dicopper core

Abstract: Dicopper(II) complexes of a series of different pyrazolate-based dinucleating ligands [L1](-)-[L4](-) have been synthesized and characterized structurally and spectroscopically. A major difference between the four complexes is the individual metal-metal separation that is enforced by the chelating side arms of the pyrazolate ligand scaffold: it varies from 3.45 A in 2 x (BF4)4 to 4.53 A in 4 x (ClO4)2. All complexes have been evaluated as model systems for the catechol oxidase enzyme by using 3,5-di-tert-butylcatechole (DTBC) as the test substrate. They were shown to exhibit very different catecholase activities ranging from very efficient to poor catalysts (k(obs) between 2430+/-202 and 22.8+/-1.2 h(-1)), with an order of decreasing activity 2 x (ClO4)4 > 1 x (ClO4)2 > 3 x (ClO4)2 >> 4 x (ClO4)2. A correlation of the catecholase activities with the variation in Cu...Cu distances, as well as other effects resulting from the distinct redox potentials, neighboring groups, and the individual coordination spheres are discussed. Saturation behavior for the rate dependence on substrate concentration was observed in only two cases, that is, for the most active 2 x (ClO4)4 and for the least active 4 x (ClO4)2, whereas a catalytic rate that is almost independent of substrate concentration (within the range studied) was observed for 1 x (ClO4)2 and 3 x (ClO4)2. H2O2 was detected as the product of O2 reduction in the catecholase reaction of the three most active systems. The structures of the adducts of "L3Cu2" and "L4Cu2" with a substrate analogue (tetrachlorocatecholate, TCC) suggest a bidentate substrate coordination to only one of the copper ions for those catalysts that feature short ligand side arms and correspondingly exhibit larger metal-metal separations; this possibly contributes to the lower activity of these systems. TCC binding is supported by several H-bonding interactions to water molecules at the adjacent copper or to ligand-side-arm N-donors; this emphasizes the importance of functional groups in proximity to the bimetallic active site.

Green Chemical Approaches toward High-Quality Semiconductor Nanocrystals

Abstract: Green chemistry principles have gradually been implemented into the development of the synthetic chemistry of high-quality semiconductor nanocrystals. In comparison with the original organometallic approach, the resulting alternative routes are safe, simple, inexpensive, reproducible, versatile, "user friendly", and yield nanocrystals with well-controlled size, shape, and size/shape distribution. Further developments in this direction will promote the understanding of crystallization in general.

Palladium Fluoride Complexes: One More Step toward Metal‐Mediated C−F Bond Formation

Abstract: The first molecular complexes of palladium containing a Pd-F bond, both fluorides and bifluorides, were synthesized and fully characterized in the solid state and in solution. Reactivity studies of the Pd fluoride complexes revealed their unexpected stability and unusual chemical properties, different from the hydroxo, chloro, bromo, and iodo analogues. A novel efficient method to generate "naked fluoride" was developed using [(Ph(3)P)(2)Pd(F)Ph]. The naked fluoride from the Pd source fluorinated dichloromethane, deprotonated chloroform, and catalyzed di- and trimerization of hexafluoropropene under uncommonly mild conditions.

Analytical determination of the [Ln-aminoxyl radical] exchange interaction taking into account both the ligand-field effect and the spin-orbit coupling of the lanthanide ion (Ln = DyIII and HoIII).

Abstract: Numerous compounds in which a paramagnetic LnIII ion is in an exchange interaction with a second spin carrier, such as a transition metal ion or an organic radical, have been described. However, except for GdIII, very little has been reported about the magnitude of the interactions. Indeed, for these ions both the ligand-field effects and the exchange interactions between the magnetic centers become relevant in the same temperature range; this makes the analysis of the magnetic behavior of such compounds more difficult. In this study, quantitative analyses of the thermal variations of the static isothermal initial magnetic susceptibility measured on powdered samples of the {Ln(NO3)3[organic radical]2} (Ln=DyIII and HoIII) compounds were performed. The ligand-field effects on the Ln ions were taken into account, and the exchange interactions within a molecule were treated exactly within an appropriate Racah formalism. Values of the intramolecular {Ln–aminoxyl radical} exchange parameter have thus been rigorously deduced for both the Dy Kramers and Ho non-Kramers ion-based compounds. Ferromagnetic {Ln–radical} interactions are found for both the Dy and Ho derivatives with J=8 cm−1 and J=4.5 cm−1, respectively.

Three novel interpenetrating diamondoid networks from self-assembly of 1,12-dodecanedinitrile with silver(I) salts.

Abstract: The self-assemblyof 1,12-do- decanedinitrile (ddn) with various silver salts (NO3 ,P F 6 ,A sF 6 ,C lO 4) afford- ed new polymeric coordination net- works with the general formula (Ag(ddn)2)X. All these species contain interpenetrating diamondoid nets show- ing interesting features: with X NO3 the cationic (Ag(ddn)2) network exhib- its the highest interpenetration (tenfold) ever found within diamondoid nets ex- clusivelybased on coordinative bonds. When X PF6 or AsF6 an eightfold diamondoid network is obtained that shows an unusual (44) mode of inter- penetration, instead of the ™normal∫ set of eight nets equallytranslated along a principal axis of the adamantanoid cag- es. The polymeric species that forms with X ClO4 is a fourfold interpene- trating diamondoid network; the lower degree of interpenetration in this case is related to the conformation assumed by the flexible ddn ligands.

The aldol addition reaction: an old transformation at constant rebirth.

Abstract: The main recent conceptual advances in asymmetric aldol reactions are presented. Methods ranging from stoichiometric chiral auxiliary-mediated to direct, catalytic reactions are covered, including the Mukaiyama aldol reactions which use stoichiometric base and silylating reagents, but catalytic (substoichiometric) amounts of the chiral inductor. The salient features of each new development are noted, paying special attention to practical concerns and to the potential implementation for large scale production. After examination of pros and cons of each strategy, gaps and limitations that deserve further investigation are highlighted.

Metalloporphyrin-mediated asymmetric nitrogen-atom transfer to hydrocarbons: aziridination of alkenes and amidation of saturated C-H bonds catalyzed by chiral ruthenium and manganese porphyrins.

Abstract: Chiral metalloporphyrins [Mn(Por*)(OH)(MeOH)] (1) and [Ru(Por*)(CO)(EtOH)] (2) catalyze asymmetric aziridination of aromatic alkenes and asymmetric amidation of benzylic hydrocarbons to give moderate enantiomeric excesses. The mass balance in these nitrogen-atom-transfer processes has been examined. With PhI=NTs as the nitrogen source, the aziridination of styrenes, trans-stilbene, 2-vinylnaphthalene, indene, and 2,2-dimethylchromene catalyzed by complex 1 or 2 resulted in up to 99 % substrate conversions and up to 94 % aziridine selectivities, whereas the amidation of ethylbenzenes, indan, tetralin, 1-, and 2-ethylnaphthalene catalyzed by complex 2 led to substrate conversions of up to 32 % and amide selectivities of up to 91 %. Complex 1 or 2 can also catalyze the asymmetric amidation of 4-methoxyethylbenzene, tetralin, and 2-ethylnaphthalene with "PhI(OAc)(2) + NH(2)SO(2)Me", affording the N-substituted methanesulfonamides in up to 56 % ee with substrate conversions of up to 34 % and amide selectivities of up to 92 %. Extension of the "complex 1 + PhI=NTs" or "complex 1 + PhI(OAc)(2) + NH(2)R (R=Ts, Ns)" amidation protocol to a steroid resulted in diastereoselective amidation of cholesteryl acetate at the allylic C-H bonds at C-7 with substrate conversions of up to 49 % and amide selectivities of up to 90 % (alpha:beta ratio: up to 4.2:1). An aziridination- and amidation-active chiral bis(tosylimido)ruthenium(VI) porphyrin, [Ru(Por*)(NTs)(2)] (3), and a ruthenium porphyrin aziridine adduct, [Ru(Por*)(CO)(TsAz)] (4, TsAz=N-tosyl-2- (4-chlorophenyl)aziridine), have been isolated from the reaction of 2 with PhI=NTs and N-tosyl-2-(4-chlorophenyl)aziridine, respectively. The imidoruthenium porphyrin 3 could be an active species in the aziridination or amidation catalyzed by complex 2 described above. The second-order rate constants for the reactions of 3 with styrenes, 2-vinylnaphthalene, indene, ethylbenzenes, and 2-ethylnaphthalene range from 3.7-42.5x10(-3) dm(3) mol(-1) s(-1). An X-ray structure determination of complex 4 reveals an O- rather than N-coordination of the aziridine axial ligand. The fact that the N-tosylaziridine in 4 does not adopt an N-coordination mode disfavors a concerted pathway in the aziridination by a tosylimido ruthenium porphyrin active species.

Chemically Induced Contraction and Stretching of a Linear Rotaxane Dimer

Abstract: Copper(I)-induced assembly of two self-complementary identical units, which consist of a ring that incorporates a 1,10-phenanthroline group attached to a small filament containing a second 1,10-phenanthroline (phen) group, leads quantitatively to a doubly threaded complex. Each copper(I) center is four-coordinate and is located inside a ring and bound to a phen from the macrocyle. The two other coordination sites are occupied by a phen from the filament connected to the other ring. An X-ray structure of the dicopper(I) complex unambiguously demonstrates the doubly threaded nature of the system. The molecule has C(2) symmetry in the crystal. This is an extended form with a Cu small middle dot small middle dot small middle dotCu separation of 18.3 A and an overall length close to 40 A. Further synthetic work, which utilizes the two terminal phenolic functions of the previous dicopper(I) complex, gives rise to a more complex system in which both filaments have been prolonged in opposite directions by 2,2':6',2"-terpyridine (terpy) motifs and bulky stoppers. The organic backbone is that of a rotaxane dimer. Although redox cycling of Cu(I) to Cu(II) did not lead to intramolecular rearrangement, simple chemical reactions induced large conformational changes. The rotaxane dimer was set in motion as follows. The dicopper(I) complex, which is in an extended conformation, was demetallated by using KCN. From the free ligand, the dizinc complex was formed quantitatively at room temperature. (1)H NMR data show that a new conformation is obtained: each Zn(II) is five-coordinate (phen + terpy), and the molecule is in a contracted conformation. This process is reminiscent of biological muscles in the sense that the two filaments of this system can be moved along one another in a gliding motion that keeps the whole system together, but which converts a stretched compound (overall length approximately equal to 83 A) into a contracted species (overall length approximately equal to 65 A, according to CPK models). The motion is quantitatively reversed by the addition of an excess of copper(I) to the dizinc complex; this regenerates the extended starting form. Although the motivation of the present contribution was to illustrate that a muscle-like molecule may be stretched or contracted using electrochemistry and coordination chemistry, the main body of the work is organic synthesis. This is testified by the fact that the dicopper(I) rotaxane dimer was obtained in 23 steps from commercially available compounds.

Mechanism of olefin metathesis with catalysis by ruthenium carbene complexes: density functional studies on model systems.

Abstract: Gradient-corrected (BP86) density functional calculations were used to study alternative mechanisms of the metathesis reactions between ethene and model catalysts [(PH(3))(L)Cl(2)Ru[double bond]CH(2)] with L=PH3 (I) and L=C(3)N(2)H(4)=imidazol-2-ylidene (II). On the associative pathway, the initial addition of ethene is calculated to be rate-determining for both catalysts (Delta G(22-25)*[double bond] kcal mol(-1)). The dissociative pathway starts with the dissociation of phosphane, which is rather facile (Delta G(298)* is approximately equal to 5-10 kcal mol(-1)). The resulting active species (L)Cl(2)Ru[double bond]CH(2) can coordinate ethene cis or trans to L. The cis addition is unfavorable and mechanistically irrelevant (Delta G(298)* is approximately equal to 21-25 kcal mol(-1)). The trans coordination is barrierless, and the rate-determining step in the subsequent catalytic cycle is either ring closure of the complex to yield the ruthenacyclobutane (catalyst I, Delta G(298)*=12 kcal mol(-1)), or the reverse reaction (catalyst II, ring opening, Delta G(298)*=10 kcal mol(-1)), that is, II is slightly more active than I. For both catalysts, the dissociative mechanism with trans olefin coordination is favored. The relative energies of the species on this pathway can be tuned by ligand variation, as seen in (PMe(3))(2)Cl(2)Ru[double bond]CH(2) (III), in which phosphane dissociation is impeded and olefin insertion is facilitated relative to I. The differences in calculated relative energies for the model catalysts I-III can be rationalized in terms of electronic effects. Comparisons with experiment indicate that steric effects must also be considered for real catalysts containing bulky substituents.

Modified guanidines as chiral auxiliaries.

Abstract: Investigations on modified guanidines, prepared by newly developed methods, as potential chiral auxiliaries led to reasonable asymmetric induction not only in catalytic but also in stoichiometric asymmetric syntheses. These guanidine-mediated reactions may contribute to the development of green chemistry because of their possible application as re-cyclable (economically favored) and easily functionalizable (widely applicable) auxiliaries.

Ruthenium-Catalyzed Transfer Hydrogenation of Imines by Propan-2-ol in Benzene

Abstract: Transfer hydrogenation of a variety of different imines to the corresponding amines by propan-2-ol in benzene catalyzed by [Ru2(CO)4(mu-H)(C4Ph4COHOCC4Ph4)] (1) has been studied. The reaction is highly efficient with turnover frequencies of over 800 per hour, and the product amines were obtained in excellent yields. A remarkable concentration dependence of propan-2-ol was observed when the reaction was run in benzene as cosolvent. An optimum was obtained at 24 equivalents of propan-2-ol to imine, and further increase of the propan-2-ol led to a dramatic decrease in rate. Also the use of polar cosolvents with 24 equivalents of propan-2-ol gave a low rate. It was found that ketimines react faster than aldimines and that electron-donating substituents on the imine increase the rate of the catalytic transfer hydrogenation. Electron-withdrawing substituents decreased the rate. An isomerization was observed with imines having an alpha-hydrogen at the N-alkyl substituent, which is in accordance with a mechanism involving a ruthenium-amine intermediate. It was demonstrated that the ruthenium-amine complex from alpha-methylbenzylamine, corresponding to the postulated intermediate, can replace 1 as catalyst in the transfer hydrogenation of imines. A primary deuterium isotope effect of kCH/CD = 2.7 +/- 0.25 was observed when 2-deuterio-propan-2-ol was used in place of propan-2-ol in the transfer hydrogenation of N-phenyl-(1-phenylethylidene)amine.

Syntheses, crystal structures, and physical properties of dinuclear copper(I) and tetranuclear mixed-valence copper(I,II) complexes with hydroxylated bipyridyl-like ligands.

Abstract: Four copper complexes with hydroxylated bipyridyl-like ligands, namely [Cu2(ophen)2] (1), [Cu4(ophen)4(tp)] (2), [Cu4(obpy)4(tp)] (3), and [Cu4(obpy)4(dpdc)]⋅2H2O (4), (Hophen=2-hydroxy-1,10-phenanthroline, Hobpy=6-hydroxy-2,2′-bipyridine, tp=terephthalate, dpdc=diphenyl-4,4′-dicarboxylate) have been synthesized hydrothermally. X-ray single-crystal structural analyses of these complexes reveal that 1,10-phenanthroline (phen) or 2,2′-bipyridine (bpy) ligands are hydroxylated into ophen or obpy during the reaction, which provides structural evidence for the long-time argued Gillard mechanism. The dinuclear copper(I) complex 1 has three supramolecular isomers in the solid state, in which short copper–copper distances (2.66–2.68 A) indicate weak metal–metal bonding interactions. Each of the mixed-valence copper(i,ii) complexes 2–4 consists of a pair of [Cu2(ophen)2]+ or [Cu2(obpy)2]+ fragments bridged by a dicarboxylate ligand into a neutral tetranuclear dumbbell structure. Dinuclear 1 is an intermediate in the formation of 2 and can be converted into 2 in the presence of additional copper(II) salt and tp ligands under hydrothermal conditions. In addition to the ophen-centered π→π* excited-state emission, 1 shows strong emissions at ambient temperature, which may be tentatively assigned as an admixture of copper-centered d→s,p and MLCT excited states.