A 1,2,3-triazole-derived pincer-type mesoionic carbene complex of iron(II): carbonyl elimination and hydrosilylation of aromatic aldehydes via the concerted reaction with hydrosilane and a base.

Iron complexes bearing 1,2,3-triazol-5-ylidene were synthesized and applied to the reaction with hydrosilane and homogeneous catalytic hydrosilylation of aromatic ketones and aldehydes. Addition of a free carbene to a solution of Fe(CO)4Br2 yielded an octahedral, diamagnetic and cationic iron(II) complex [Fe(1,2,3-triazolylidene)(CO)2Br]+. Pyrolysis of the dicarbonyl complex eliminated the two CO ligands to form a paramagnetic four-coordinate complex. A theoretical study using DFT calculations indicated that the spin state changed from singlet to quintet during ligand elimination. Investigations of the successful hydrosilylation of acetophenone and benzaldehyde derivatives using MIC-iron(II) bromide suggested the importance of the base for efficient conversion in the catalytic process. The bromide-to-hydride exchange reaction, transmetallation, of MIC-iron(II) bromide in the presence of KOtBu and HSi(OEt)3 which could occur in the initial process of hydrosilylation was proposed, and supported by a theoretical study.

Photo-induced Morphological Changes of Lipid Bilayer Vesicles Enabled by a Visible-Light-Responsive Azo Compound.

Living cells and organelles are separated by a lipid membrane bilayer. It is possible to induce morphological changes in this membrane by disturbing the order of the membrane using external stimuli and understanding the details of this mechanism is expected to be applicable to intracellular transport. DBA (DBAB-BODIPY-aminopropyl), which contains (1) a DBAB (4-[di(biphenyl-4-yl)amino]azobenzene) moiety that undergoes photo-isomerization under visible light irradiation, and (2) a BODIPY (borondipyrromethene) fluorophore was synthesized. The π-π* transition absorptions of both the azo moiety and that of BODIPY moiety in DBA were observed, independently. The photo-isomerization rate constant of the DMSO solution of DBA at 299K is 5.5 ×10-3/s. The structure of the fluorescent group in DBA did not readily influence the isomerization. Upon introducing DBA into the lipid bilayer membranes of a vesicle suspension and irradiating the vesicles with visible light to isomerize the azo group, a morphological change in of the vesicles was observed due to the disturbance of the membrane order. Thus, DBA is a useful molecule for artificial modulation of the lipid membrane morphology.

Well-Defined NHC-Ni Complexes as Catalysts: Preparation, Structures and Mechanistic Studies in Cross-Coupling Reactions.

Developmental studies are ongoing to discover a way to utilise new N-heterocyclic carbene (NHC)-Ni complexes as catalysts. Using a bulky NHC ligand, it is possible to synthesise an NHC/phosphine-mixed heteroleptic Ni(II) complex, which can serve as an excellent catalyst for various cross-coupling reactions. During the study of the reaction mechanisms using these Ni complexes, NHC-Ni(I) complexes were accidentally discovered, and it was observed that they exhibit excellent catalytic activity for cross-coupling reactions. The possibility of the presence of NHC-Ni(I) intermediates in these catalytic reaction pathways has been experimentally demonstrated. Depending on the type of reaction, dinuclear Ni(I) and mononuclear Ni(I) complexes can function as intermediates. The results of the investigation of each reaction mechanism are summarised, and the prospects are described.

Fluorine-Substituted Arylphosphine for an NHC-Ni(I) System, Air-Stable in a Solid State but Catalytically Active in Solution.

Monovalent NHC-nickel complexes bearing triarylphosphine, in which fluorine is incorporated onto the aryl groups, have been synthesized. Tris(3,5-di(trifluoromethyl)-phenyl)phosphine efficiently gave a monovalent nickel bromide complex, whose structure was determined by X-ray diffraction analysis for the first time. In the solid state, the Ni(I) complex was less susceptible to oxidation in air than the triphenylphosphine complex, indicating greatly improved solid-state stability. In contrast, the Ni(I) complex in solution can easily liberate the phosphine, high catalytic activity toward the Kumada-Tamao-Corriu coupling of aryl bromides.

Buchwald-Hartwig Amination of Phosphinines and the Effect of Amine Substituents on Optoelectronic Properties of the Resulting Coupling Products.

The Buchwald-Hartwig amination of a phosphinine bearing a bromophenyl moiety was carried out using a dinuclear Ni catalyst. A variety of monoarylamines, diarylamines, and alkylamine, as well as heterocycles, were successfully converted into novel phosphinines bearing amine units. The photophysical properties of these novel phosphinines were examined, including the substituent-dependent absorption/emission features and intramolecular charge-transfer interactions.

Dinuclear Nickel(I) and Palladium(I) Complexes for Highly Active Transformations of Organic Compounds.

In typical catalytic organic transformations, transition metals in catalytically active complexes are present in their most stable valence states, such as palladium(0) and (II). However, some dimeric monovalent metal complexes can be stabilized by auxiliary ligands to form diamagnetic compounds with metal-metal bonding interactions. These diamagnetic compounds can act as catalysts while retaining their dimeric forms, split homolytically or heterolytically into monomeric forms, which usually have high activity, or in contrast, become completely deactivated as catalysts. Recently, many studies using group 10 metal complexes containing nickel and palladium have demonstrated that under specific conditions, the active forms of these catalyst precursors are not mononuclear zerovalent complexes, but instead dinuclear monovalent metal complexes. In this mini-review, we have surveyed the preparation, reactivity, and the catalytic processes of dinuclear nickel(I) and palladium(I) complexes, focusing on mechanistic insights into the precatalyst activation systems and the structure and behavior of nickel and palladium intermediates.

Bimetallic Cu(I) complex with a pyridine-bridged bis(1,2,3-triazole-5-ylidene) ligand.

A dinuclear copper(i) complex bearing a mesoionic carbene ligand has been prepared from the corresponding silver analogue and its structure determined spectroscopically. The results revealed that two Cu(i) halide salt molecules were bound to the carbon atoms of the pyridine-bridged bis(triazolylidene) moieties rather than the pyridine. Cyclic voltammogram measurements revealed that the two Cu(i) centres underwent a stepwise oxidation, suggesting that both the triazolylidene rings of the ligand could be on the same expanded π-conjugated system. The catalytic hydroboration of styrene derivatives with bis(pinacolato)diborane in the presence of this complex allowed for the ß-selective formation of the corresponding alkylboronate esters.

Structure-activity relationship of indolicidin, a Trp-rich antibacterial peptide.

A series of Trp and Arg analogs of antibacterial indolicidin (Ind) was synthesized and the antimicrobial and hemolytic activities were investigated. [L(9)]Ind, [L(11)]Ind, [K(8),L(9)]Ind and [K(6, 8),L(9)]Ind showed desirable characteristics, exhibiting negligible hemolytic activity while keeping strong antibacterial activity. The results indicated that the Trp residue at position 11 essentially contributes to both activities and one can not be exchanged for the other, whereas the Trp residues at positions 4 and 9 play important roles in antimicrobial and hemolytic activities, respectively. The Trp residues at positions 6 and 8 play no important roles in biological activities. We then found that the retro analog of Ind showed higher antibacterial activity than Ind against both Gram-positive and Gram-negative bacteria but remarkably lower hemolytic activity than that of Ind.

A new aspect of nickel-catalyzed Grignard cross-coupling reactions: selective synthesis, structure, and catalytic behavior of a T-shape three-coordinate nickel(I) chloride bearing a bulky NHC ligand.

Novel T-shape three-coordinate nickel(I) chlorides bearing an N-heterocyclic carbene ligand, NiCl(IPr)(2) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene), were isolated by a reaction of Ni(0)(NHC)(2) with aryl chlorides. This Ni(I) complex was shown to act as a catalyst in a cross-coupling reaction of aryl halides with phenylmagnesium chloride.

C-F bond-cleavage reactions of fluoroalkanes with magnesium reagents and without metal catalysts.

An unexpected C-F bond-cleavage reaction of unactivated fluoroalkanes with the well-known Grignard reagents without using metal catalysts has been discovered. For example, a reaction between 1-fluorooctane and phenyl magnesium chloride gave n-octylbenzene in moderate yield. This coupling reaction via the activation of an unactivated alkyl carbon-fluorine bond proceeds with phenylmagnesium chloride, whereas methylmagnesium chloride did not give the C-C cross-coupling product but rather a halogen exchange product.

Nickel-NHC-catalyzed alpha-arylation of acyclic ketones and amination of haloarenes and unexpected preferential N-arylation of 4-aminopropiophenone.

Arylation of both acyclic ketones and primary and secondary amines was achieved using a new, simple, stable, and easy-to-access nickel(II)-halide complex bearing mixed PPh3/N-heterocyclic carbene ligands as a catalyst precursor. Acyclic ketones were first arylated at the alpha-position with the nickel catalyst. On the other hand, less basic amines, such as diphenylamine and 4-aminobenzophenone, were more favorable in the catalytic amination of haloarenes than basic amines, contrary to previous reports. N-Arylation of 4-aminopropiophenone was found to proceed selectively without causing alpha-arylation of the ketone group.

Organoruthenium(II) and (III) amidinates, (eta5-C5Me5)Ru(eta-amidinate) and (eta5-C5Me5)RuCl(eta-amidinate), as unique redox catalysts for the intramolecular Kharasch reactions: facile access to a pyrrolizidine alkaloid skeleton under mild conditions.

A novel organoruthenium(III) amidinate, (eta5-C5Me5)RuCl(eta-iPrN=C(Me)NiPr) (2), has been prepared by oxidation of organoruthenium amidinate, (eta5-C5Me5)Ru(eta-iPrN=C-(Me)NiPr) (1), by organic chlorides; both 1 and 2 are found to be good catalysts for atom-transfer cyclization of N-allyltrichloroacetamides which are useful for successful preparation of a pyrrolizidine alkaloid skeleton under mild conditions.

A triruthenium carbonyl cluster bearing a bridging acenaphthylene ligand: an efficient catalyst for reduction of esters, carboxylic acids, and amides by trialkylsilanes.

An efficient reduction of carboxylic acids, esters, and amides with trialkylsilanes is accomplished using a triruthenium carbonyl cluster bearing a bridging acenaphthylene ligand, (mu(3),eta(2):eta(3):eta(5)-acenaphthylene)Ru(3)(CO)(7), as the catalyst. Preactivation of the catalyst by hydrosilanes accelerates the reactions. Sterically small trialkylsilanes are effective in these reactions. Reduction of carboxylic acids and amides efficiently produces the corresponding silyl ethers and amines, respectively. Reduction of esters gives a mixture of silyl and alkyl ethers, but can be controlled by changing the silanes and solvents.

Novel coordinatively unsaturated bimetallic complexes, [(eta5-C5Me5)Ru(mu2-iPrNC(Me)=N(i)Pr)Ru(eta5-C5Me5)]+: a bridging amidinate ligand perpendicular to the metal-metal axis effectively stabilizes the highly reactive cationic diruthenium species.

Coordinatively unsaturated diruthenium complexes, [(eta5-C5Me5)Ru(mu2-iPrNC(Me)=NiPr)Ru(eta5-C5Me5)]+, of which crystallography revealed structures bearing a bridging amidinate ligand perpendicular to the Ru-Ru axis, were synthesized by anion exchange of [(eta5-C3Me5(Ru(mu2-iPrNC(Me)=NiPr)Ru(eta5-C5Me5)]+ Br- by weakly coordinating anions. Variable-temperature NMR showed rapid motion of the bridging amidinate ligand. The coordinatively unsaturated nature of the cationic complexes provides their high reactivity toward a series of two electron donor ligands. Oxidative addition of molecular hydrogen occurred to give [(eta5-C5Me5)Ru(mu2-iPrNC(Me)=NiPr)(mu-H)Ru(eta5-C5Me5)(H)]+, which was isolated and characterized.

Triarylation of eta 6-dihydronaphthalene-Cr(CO)3 complexes.

With ease, eta 6-dihydronaphthalene tricarbonylchromium(0) complexes undergo a triple arylation with concomitant ring closure, when submitted to Heck reactions under 'Jeffery conditions'.