Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal–organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

Selective gas adsorption and separation in metal–organic frameworks

B. Anionic Ligands 302 IX. Group 9 Catalysts 302 X. Group 10 Catalysts 303 A. Neutral Ligands 303 1. R-Diimine and Related Ligands 303 2. Other Neutral Nitrogen-Based Ligands 304 3. Chelating Phosphorus-Based Ligands 304 B. Monoanionic Ligands 305 1. [PO] Chelates 305 2. [NO] Chelates 306 3. Other Monoanionic Ligands 306 4. Carbon-Based Ligands 306 XI. Group 11 Catalysts 307 XII. Group 12 Catalysts 307 XIII. Group 13 Catalysts 307 XIV. Summary and Outlook 308 XV. Glossary 308 XVI. References 308

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Advances in non-metallocene olefin polymerization catalysis.

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

One of the most exciting developments in the areas of catalysis, organometallic chemistry, and polymer science in recent years has been the intense exploration and commercialization of new polymerization technologies based on single-site and metallocene coordination olefin polymerization catalysts.1 The vast number of specifically designed/synthesized transition metal complexes (catalyst precursors) and main-group organometallic compounds (cocatalysts) allows unprecedented control over polymer microstructure, the generation of new polymer architectures, and the development of new polymerization reactions. Commercialization of new generations of single-site and metallocene catalyst-based technologies has provided the multibillion pound per year polyolefins industry with the ability to deliver a wide range of new and innovative olefin-based polymers having improved properties.2-4 The intense industrial activity in the field and the challenges to our basic understanding that have come to light have in turn 1391 Chem. Rev. 2000, 100, 1391−1434

/pdf/cocatalysts-for-metal-catalyzed-olefin-polymerization-37a9jvjiei.pdf

Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure−Activity Relationships

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

The reaction of dihydrogen with a side-on bound dinitrogen complex of zirconium was investigated. Instead of a displacement of the dinitrogen moiety, which is the common mode of reactivity, a complex containing both a bridging hydride and a bridging hydrazido unit with a nitrogen-hydrogen bond was observed. This reaction was extended to primary silanes to produce a species that contained a nitrogen-silicon bond. In addition, an intermediate in the dihydrogen addition has been structurally characterized as having a bridging dihydrogen unit.

https://science.sciencemag.org/content/sci/275/5305/1445.full.pdf

Transformation of Coordinated Dinitrogen by Reaction with Dihydrogen and Primary Silanes

Synthesis and Structures of Mono- and Bis(amidinate) Complexes of Aluminum

Oxide materials with open structures have been the subject of intense research for decades, because of their economically important applications including catalysis, separations, waste removal, and water softening. The now classical materials are the aluminosilicate zeolites whose structures are based on frameworks of corner-sharing metal -oxygen tetrahedra. 1 The pores in such materials are characterized by the size of the rings defining them, which in turn are measured by the number of metal atoms in the ring. Traditionally, rings of 8, 10, or 12 metal atoms have been denoted as small, medium, and large. The discovery 2

A flexible germanate structure containing 24-ring channels and with very low framework density.

Crystal Structure Analysis of a Synthetic Non‐Heme Diiron ? O2 Adduct: Insight into the Mechanism of Oxygen Activation

The reactivity of dicopper(I) complexes of the ligands α,α‘-bis(4,7-diisopropyl-1,4,7-triazacyclononan-1-yl)-p- and m-xylene (p- and m-XYLiPr4) with dioxygen was examined by spectroscopic and rapid...

Binucleating Ligand Structural Effects on (μ-Peroxo)- and Bis(μ-oxo)dicopper Complex Formation and Decay: Competition between Arene Hydroxylation and Aliphatic C−H Bond Activation

Victor G. Young

Papers

Transformation of Coordinated Dinitrogen by Reaction with Dihydrogen and Primary Silanes

Synthesis and Structures of Mono- and Bis(amidinate) Complexes of Aluminum

A flexible germanate structure containing 24-ring channels and with very low framework density.

Crystal Structure Analysis of a Synthetic Non‐Heme Diiron ? O2 Adduct: Insight into the Mechanism of Oxygen Activation

Binucleating Ligand Structural Effects on (μ-Peroxo)- and Bis(μ-oxo)dicopper Complex Formation and Decay: Competition between Arene Hydroxylation and Aliphatic C−H Bond Activation