This critical review will be of interest to the experts in porous solids (including catalysis), but also solid state chemists and physicists. It presents the state-of-the-art on hybrid porous solids, their advantages, their new routes of synthesis, the structural concepts useful for their ‘design’, aiming at reaching very large pores. Their dynamic properties and the possibility of predicting their structure are described. The large tunability of the pore size leads to unprecedented properties and applications. They concern adsorption of species, storage and delivery and the physical properties of the dense phases. (323 references)

Hybrid porous solids: past, present, future

N-Heterocyclic Carbenes in Late Transition Metal Catalysis

Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.

Molecular self-assembly and nanochemistry: A chemical strategy for the synthesis of nanostructures

Dioxygen activation at mononuclear nonheme iron active sites: enzymes, models, and intermediates.

8.4.5. Nitromercuration Reactions 3878 9. Hydroamination of Alkenes and Alkynes under Microwave Irradiation 3878 * To whom correspondence should be addressed. Phone: +49 241 8

Hydroamination: direct addition of amines to alkenes and alkynes.

The effects of hydrogen bonding and hydrophobic field on the thermal stabilities of Cu(II)-OOH complexes have been studied using tripodal tetradentate ligands with their functional groups on the basis of UV-vis, ESR, ESI-mass, and resonance Raman spectroscopies.

Thermal Stability of Mononuclear Hydroperoxocopper(II) Species. Effects of Hydrogen Bonding and Hydrophobic Field

Eight adducts of Rh2(O2CCH3)4 with axial pyridine derivatives that contain hydrogen-bonding amino and/or steric methyl substituents in the 2- and 6-positions have been prepared and examined by electronic absorption and 1H NMR spectroscopy in solution and by elemental, IR, thermogravimetric, and X-ray diffraction analyses in the solid state. The results indicated that strong hydrogen bonding interactions between Rh2(O2CCH3)4 and axially coordinated pyridine derivatives with a 2- or 6-amino group occur in both solution and the solid state and contribute to the higher thermal stability of the molecular assembly of dirhodium complexes. It was demonstrated that such a combination of coordinate and hydrogen bonds is useful as a building tool in designing and constructing new organic-inorganic hybridized compounds and supramolecular architectures.

Syntheses, structures, and properties of tetrakis(mu-acetato)dirhodium(II) complexes with axial pyridine nitrogen donor ligands with or without assistance of hydrogen bonds.

Mononuclear copper complexes with a tripodal tetradentate ligand, tris(6-pivaloylamino-2-pyridylmethyl)amine (Htppa), and several anions have been prepared as a model metal centre of copper enzymes, whose structures have been examined by electronic absorption, ESR and NMR spectral, cyclic voltammetry, and X-ray diffraction methods. Those with an anion such as OH−, Cl−, Br−, and I− were shown to form a trigonal-bipyramidal geometry. The X-ray structures of [Cu(Htppa)](ClO4)2·2H2O·CH3OH, [CuCl(Htppa)]ClO4, [Cu(OH)(Htppa)]ClO4, [Cu(OH)(tppa)], and [Cu(tppa)](BPh4), obtained as a single crystal, revealed all trigonal-bipyramidal geometry with four nitrogen atoms of Htppa in trigonal plane and axial position and with the anion in another apical position. The reaction with NaN3 gave [Cu(N3)2(Htppa)], whose crystal structure was a square-pyramid with three nitrogen atoms of Htppa and N3− in square-planar positions and with another N3− in apical position. The redox potentials of [CuCl(Htppa)]ClO4 in MeCN or CH2Cl...

Preparations, Structures, and Properties of Cu(II) Complexes with Tripodal Tetradentate Ligand, Tris(6-pivaloylamino-2-pyridylmethyl)amine (Htppa), and Reaction of Its Cu(I) Complex with Dioxygen.

Ruthenium(II) complexes, [Ru(babp)(dmso)L], consisting of tetradentate square-planar ligand (babp = 6,6′-bis(benzoylamino)-2,2′-bipyridinato) and two monodentate axial ones, DMSO and L (L = dmso or...

Koichiro Jitsukawa

Papers

Thermal Stability of Mononuclear Hydroperoxocopper(II) Species. Effects of Hydrogen Bonding and Hydrophobic Field

Syntheses, structures, and properties of tetrakis(mu-acetato)dirhodium(II) complexes with axial pyridine nitrogen donor ligands with or without assistance of hydrogen bonds.

Preparations, Structures, and Properties of Cu(II) Complexes with Tripodal Tetradentate Ligand, Tris(6-pivaloylamino-2-pyridylmethyl)amine (Htppa), and Reaction of Its Cu(I) Complex with Dioxygen.

Characteristics of Mononuclear Ruthenium–Oxo Complexes Adjusted by Axial Ligand for the Catalysis of Oxygen-Transfer Reactions

Preparation of a Hydroperoxo Zinc(II) Intermediate