3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical Routes for the Transformation of Biomass into Chemicals

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

Great attention is currently paid to the synthesis of polynuclear transition metal complexes and the study of their photochemical, photophysical, and electrochemical properties. This interest is stimulated, in particular, by attempts to design and construct multicomponent systems (often called supramolecular species) capable of performing useful lightand/or redox-induced functions.1-16 A great deal of investigations on mononuclear transition metal complexes had previously shown that several families of these compounds are very interesting from the electrochemical, photochemical, and photophysical viewpoints.17-22 The metalligand interaction, in fact, is often (i) weak enough to allow the manifestation of intrinsic properties of metal and ligands (e.g., ligand-centered and metalcentered absorption bands and redox waves) and, at the same time, (ii) strong enough to cause the appearance of new properties, characteristic of the whole compound (e.g., metal-to-ligand or ligand-tometal charge-transfer bands). On passing from mononuclear to polynuclear transition metal complexes, the situation becomes even more interesting because in the latter (supramolecular) compounds one can find, besides properties related to each metal-based component, properties related to the structure and composition of the whole array. A suitable choice of the mononuclear building blocks and bridging ligands and an appropriate design of the (supramolecular) structure can in fact allow the occurrence of very interesting and potentially useful processes such as energy transfer along predetermined pathways, photoinduced charge separation, multielectron exchange at a predetermined potential, etc. The knowledge on the luminescence and redox properties of polynuclear transition metal complexes is rapidly accumulating, but it is disperse in a great number of journals. We have made an attempt to collect the available results, and we present them together with some fundamental introductory concepts and a few comments. One of the main problems, of course, was to delimit the field of this review. Using personal criteria which are related to our own research interests, we decided to consider only polynuclear transition metal complexes that can be defined as supramolecular species (section 2.2) and that are reported to exhibit luminescence. For such compounds only, the electrochemical properties have also been reviewed. Furthermore, we decided to include only classical (Werner-type) polynuclear transition metal compounds where the number of metal-based units is exactly known and the connection between the metal centers is provided only by bridging ligands. Thus, a number of interesting systems such as polymer-appended metal † In memoriam of Mauro Ciano. 759 Chem. Rev. 1996, 96, 759−833

Luminescent and Redox-Active Polynuclear Transition Metal Complexes.

Starting from the early 1990’s, the chemistry of polyvalent iodine organic compounds has experienced an explosive development. This surging interest in iodine compounds is mainly due to the very useful oxidizing properties of polyvalent organic iodine reagents, combined with their benign environmental character and commercial availability. Iodine(III) and iodine(V) derivatives are now routinely used in organic synthesis as reagents for various selective oxidative transformations of complex organic molecules. Several areas of hypervalent organoiodine chemistry have recently attracted especially active interest and research activity. These areas, in particular, include the synthetic applications of 2-iodoxybenzoic acid (IBX) and similar oxidizing reagents based on the iodine(V) derivatives, the development and synthetic use of polymer-supported and recyclable polyvalent iodine reagents, the catalytic applications of organoiodine compounds, and structural studies of complexes and supramolecular assemblies of polyvalent iodine compounds.

The chemistry of polyvalent iodine has previously been covered in four books1–4 and several comprehensive review papers.5–17 Numerous reviews on specific classes of polyvalent iodine compounds and their synthetic applications have recently been published.18–61 Most notable are the specialized reviews on [hydroxy(tosyloxy)iodo]benzene,41 the chemistry and synthetic applications of iodonium salts,29,36,38,42,43,46,47,54,55 the chemistry of iodonium ylides,56–58 the chemistry of iminoiodanes,28 hypervalent iodine fluorides,27 electrophilic perfluoroalkylations,44 perfluoroorgano hypervalent iodine compounds,61 the chemistry of benziodoxoles,24,45 polymer-supported hypervalent iodine reagents,30 hypervalent iodine-mediated ring contraction reactions,21 application of hypervalent iodine in the synthesis of heterocycles,25,40 application of hypervalent iodine in the oxidation of phenolic compounds,32,34,50–53,60 oxidation of carbonyl compounds with organohypervalent iodine reagents,37 application of hypervalent iodine in (hetero)biaryl coupling reactions,31 phosphorolytic reactivity of o-iodosylcarboxylates,33 coordination of hypervalent iodine,19 transition metal catalyzed reactions of hypervalent iodine compounds,18 radical reactions of hypervalent iodine,35,39 stereoselective reactions of hypervalent iodine electrophiles,48 catalytic applications of organoiodine compounds,20,49 and synthetic applications of pentavalent iodine reagents.22,23,26,59

The main purpose of the present review is to summarize the data that appeared in the literature following publication of our previous reviews in 1996 and 2002. In addition, a brief introductory discussion of the most important earlier works is provided in each section. The review is organized according to the classes of organic polyvalent iodine compounds with emphasis on their synthetic application. Literature coverage is through July 2008.

Chemistry of Polyvalent Iodine

This review describes a multidimensional treatment of molecular recognition phenomena involving aromatic rings in chemical and biological systems. It summarizes new results reported since the appearance of an earlier review in 2003 in host-guest chemistry, biological affinity assays and biostructural analysis, data base mining in the Cambridge Structural Database (CSD) and the Protein Data Bank (PDB), and advanced computational studies. Topics addressed are arene-arene, perfluoroarene-arene, S⋅⋅⋅aromatic, cation-π, and anion-π interactions, as well as hydrogen bonding to π systems. The generated knowledge benefits, in particular, structure-based hit-to-lead development and lead optimization both in the pharmaceutical and in the crop protection industry. It equally facilitates the development of new advanced materials and supramolecular systems, and should inspire further utilization of interactions with aromatic rings to control the stereochemical outcome of synthetic transformations.

Aromatic rings in chemical and biological recognition: energetics and structures.

A brief overview is given of platinum anticancer drugs in routine clinical use and under clinical development worldwide. Details of the binding of these drugs with nucleic acids, the preferred binding site, etc. are discussed as well. Using the mechanistic knowledge at the molecular level, in particular DNA binding, possibilities for new drugs are explored. A major part of the review deals with design, synthesis and biochemical/biophysical studies of such new compounds and their possible applications as cytostatic drugs. Special attention is given to the application of bifunctionality in such new compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Platinum Anticancer Coordination Compounds: Study of DNA Binding Inspires New Drug Design

The controlled oxidation of C–H bonds is one of the most challenging and difficult reactions in organic chemistry. Generally, it requires either stoichiometric amounts of toxic heavy metal salts or very expensive catalysts containing transition metals such as palladium, rhodium or ruthenium. The scientific community used to focus their investigations towards these relatively rare and costly elements while neglecting to look at how Nature performs these types of reactions. Biological systems only employ abundantly available metals like iron, zinc and copper. This review summarizes the background and the state of the art of enzymatic and biomimetic oxidation catalysts involving copper as the active metal center. Recent developments have shown the first very promising results in this incipient field.

Homogeneous bio-inspired copper-catalyzed oxidation reactions

Interest in supramolecular chemistry has grown significantly during the past two decades. In this context, hydrogen bonding and/or coordinative interactions have been extensively used to generate self-assembled one-, two- or three-dimensional polymeric networks. Crystal structure prediction has progressed tremendously, and the challenge for the contemporary supramolecular chemist is now to produce custom-made functional (and multifunctional) materials involving intermolecular interactions. Since the early 1990s, 1,3,5-triazine derivatives have shown their potential as building blocks for the preparation of such materials. In this microreview, a selection of outstanding examples of supramolecular networks involving the 1,3,5-triazine unit are discussed, illustrating the possibility of forming remarkable architectures by means of coordination and/or hydrogen bonds and their applications in host–guest chemistry, catalysis, anion recognition, sensoring, electronics and magnetism. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

1,3,5-Triazine-Based Synthons in Supramolecular Chemistry

Preparation, spectres RMN et proprietes electrochimiques de [Ru(bpy)2(bpt)] + et [(Ru(bpy) 2 ) 2 (bpt)] 3+

Synthesis and spectroscopic and electrochemical properties of mononuclear and dinuclear bis(2,2'-bipyridyl)ruthenium complexes containing 3,5-bis(pyridin-2-yl)-1,2,4-triazole

The heterodinuclear compounds ((bpy){sub 2}Ru(bpt)Os(bpy){sub 2})(PF{sub 6}){sub 3} (RuOs) and ((bpy){sub 2}Os(bpt)Ru(bpy){sub 2})(PF{sub 6}){sub 3} (OsRu), where Hbpt = 3,5-bis(pyridin-2-yl)-1,2,4-triazole and bpy = 2,2{prime}-bipyridine, have been prepared and characterized. The crystal and molecular structures of ((Ru(bpy){sub 2}){sub 2}(bpt))(CF{sub 3}SO{sub 3}){sub 3}{center dot}4H{sub 2}O and ((bpy){sub 2}Ru(bpt)Os(bpy){sub 2})(CF{sub 3}SO{sub 3}){sub 3}{center dot}4H{sub 2}O have been determined. Only one of the two possible geometrical isomers of the ruthenium dinuclear compound was found in the crystal structure. The two metal centers are coordinated via N(1) and N(4) of the triazole ring. The metal-metal distance is 6.184 (2) {angstrom}. The NMR data revealed that the OsRu isomer has a similar structure, but with the osmium center bound via N(1) and the ruthenium ion coordinated via N(4) of the triazole ring. The electrochemical potentials of the two heterodinuclear compounds are significantly different; for the RuOs compound the oxidation potentials are 0.73 and 1.20 V, while for the OsRu isomer the oxidation potentials are at 0.65 and 1.30 V vs SCE. These differences in electrochemical behavior between the two isomeric RuOs and OsRu compounds suggest that the N(1) atom of the triazole ring is a better {sigma}-donor than N(4). The mixed-valence dinuclear systems all exhibit rathermore » intense intervalence transition (IT) bands in the near-infrared region, suggesting a moderately strong metal-metal interaction for the bpt systems. A correlation between the energy of the IT bands of the mixed-valence dinuclear complexes and the oxidation potentials has been observed.« less

Synthesis, x-ray structure, and spectroscopic and electrochemical properties of novel heteronuclear ruthenium-osmium complexes with an asymmetric triazolate bridge

Jan Reedijk

Papers

Platinum Anticancer Coordination Compounds: Study of DNA Binding Inspires New Drug Design

Homogeneous bio-inspired copper-catalyzed oxidation reactions

1,3,5-Triazine-Based Synthons in Supramolecular Chemistry

Synthesis and spectroscopic and electrochemical properties of mononuclear and dinuclear bis(2,2'-bipyridyl)ruthenium complexes containing 3,5-bis(pyridin-2-yl)-1,2,4-triazole

Synthesis, x-ray structure, and spectroscopic and electrochemical properties of novel heteronuclear ruthenium-osmium complexes with an asymmetric triazolate bridge