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A new efficient method for the synthesis of dicompartmental ligands enalH 2 8 and of tnalH2, 10 is described. This method is essentially a concise one-step route via the Mannich condensation, from 4-methyl 2-formylphenol and paraformaldehyde with appropriate amines. A series of macrocyclic heterobimetallic complexes of type [Mc(tntnam)M o](PF6)n and [Mc'(tntnim)Ni](PF 6)n where Mc = Co(III) and Zn(II), Mc ' = Co(II), Co(III) and Zn(II) and Mo = Ni(II), Cu(II) and Zn(II) have been synthesized and characterized. The macrocyclic ligands tntnim 12 and tntnam 13 contain two geometrically distinct 6-coordinate (closed-site) and 4-coordinate (open-site) compartments which are bridged by phenolic oxygens. The heterobimetallic complexes with Zn(II) or Ni(II) in the open-site are primarily formed as 5-coordinate with a chloride ion as a fifth ligand; the latter can be removed by Ag+ ion. The 1H NMR and 13C NMR of diamagnetic complexes and [Co(tntnam)ZnCl](PF6)2, 27 and [Co(tntnam)Zn](PF6)3, 28 demonstrate that the expected trans pyridine structures are formed. Solution magnetic moments of heterobimetallic complexes indicate that all Co(III) ions are spin paired, but the Ni(II) ions are spin free. The electronic absorption and emission spectra and redox couples are reported. The crystal structures of [Zn(tntnim)NiCl]PF 6C2H5OH, 16, [Zn(tntnam)Ni](PF 6)2, 22, [Zn(tntnam)Cu](PF6) 2, 23, and [Co(tnmam)Ni(H2O)](PF6) 34H2O, 25 were determined. The crystal structures demonstrate that the expected 'trans' pyridine structures are formed. Photoreactivity of heterobimetallic complexes towards molecular oxygen showed that, in spite of sensitivity of these complexes to molecular oxygens no singlet molecular oxygen, O2 (1[Delta]g), or peroxide species were generated as a result of irradiation with visible light. A series of acyclic ligands analogous to the dialdehyde ligand enalH 2, but containing different ligating groups instead of the aldehyde moieties were prepared. These include dial.
Written by world-class authors, this most recent major book on the topic highlights new and current trends as well as future directions. It is comprehensive in its scope, covering all aspects of gold chemistry -- from homogeneous to heterogeneous catalysis, from supramolecular assemblies to sensors and medicinal applications. The result is an invaluable work for both organic and inorganic chemists working in universities and industry, as well as material scientists.
From synthesis to applications in catalysis, material science and biology this much-needed book is the first to comprehensively present everything you need to know about palladacycles. Renowned international authors guarantee high-quality content, making this a must-have for everyone working in the field.
The UK Catalysis Hub is a consortium of universities working together on fundamental and applied research to find out how catalysts work and to improve their effectiveness. The contribution of catalysis to manufacturing contributes to almost 40% of global GDP, making development and innovation within the field integral to industry.Modern Developments in Catalysis provides a review of current research and practise on catalysis, focussing on five main themes: catalysis design, environmental catalysis, catalysis and energy, chemical transformation and biocatalysis and biotransformations. Topics range from complex reactions to the intricacies of catalyst preparation for supported nanoparticles, while chapters illustrate the challenges facing catalytic science and the directions in which the field is developing. Edited by leaders of the UK Hub, this book provides insight into one of the most important areas of modern chemistry — it represents a unique learning opportunity for students and professionals studying and working towards speeding-up, improving and increasing the rate of catalytic reactions in science and industry.
Chemistry for Sustainable Development is a collection of selected papers by the participants of the International Conference on Pure and Applied Chemistry (ICPAC 2010) on the theme of “Chemistry for Sustainable Development” held in Mauritius in July 2010. In light of the significant progresses and challenges in the development and implementation of green and sustainable chemistry, this volume reviews the recent results generated by a more efficient use of resources to minimize carbon footprints, to foster the eradication or minimisation of solvent use in chemistry, and to deliver processes which lead to increased harmony between chemistry and the environment. Chemistry for Sustainable Development is written for graduates, postgraduates, researchers in industry and academia who have an interest in the fields ranging from fundamental to applied chemistry.
The subject of dioxygen activation and homogeneous catalytic oxidation by metal complexes has been in the focus of attention over the last 20 years. The widespread interest is illustrated by its recurring presence among the sessions and subject areas of important international conferences on various aspects of bioinorganic and coordination chemistry as well as catalysis. The most prominent examples are ICCC, ICBIC, EUROBIC, ISHC, and of course the ADHOC series of meetings focusing on the subject itself. Similarly, the number of original and review papers devoted to various aspects of dioxygen activation are on the rise. This trend is due obviously to the relevance of catalytic oxidation to biological processes such as dioxygen transport, and the action of oxygenase and oxidase enzymes related to metabolism. The structural and functional modeling of metalloenzymes, particularly of those containing iron and copper, by means of low-molecular complexes of iron, copper, ruthenium, cobalt, manganese, etc., have provided a wealth of indirect information helping to understand how the active centers of metalloenzymes may operate. The knowledge gained from the study of metalloenzyme models is also applicable in the design of transition metal complexes as catalytsts for specific reactions. This approach has come to be known as biomimetic or bioinspired catalysis and continues to be a fruitful and expanding area of research.
From the contents: Robert H Crabtree: Introduction and History. - Montserrat Diéguez, Oscar Pàmies and Carmen Claver: Iridium-catalysed hydrogenation using phosphorous ligands. - David H. Woodmansee and Andreas Pfaltz: Iridium Catalyzed Asymmetric Hydrogenation of Olefins with Chiral N,P and C,N Ligands. - Ourida Saidi and Jonathan M J Williams: Iridium-catalyzed Hydrogen Transfer Reactions. - John F. Bower and Michael J. Krische: Formation of C-C Bonds via Iridium Catalyzed Hydrogenation and Transfer Hydrogenation. - Jongwook Choi, Alan S. Goldman: Ir-Catalyzed Functionalization of CH Bonds. - Mark P. Pouy and John F. Hartwig: Iridium-Catalyzed Allylic Substitution. - Daniel Carmona and Luis A. Oro: Iridium-catalyzed 1.3-dipolar cycloadditions.
With contributions from experts in supported metal catalysis, from both the industry and academia, this book presents the latest developments in characterization and application of supported metals in heterogeneous catalysis. In addition to a thorough and updated coverage of the traditional aspects of heterogeneous catalysis such as preparation, characterization and use in well-established technologies such as Naphtha reforming, the book also includes emerging areas where supported metal catalysis will make significant contributions in future developments, such as fuel cells and fine chemicals synthesis. The second edition of Supported Metals in Catalysis comes complete with new and updated chapters containing important summaries of research in a rapidly evolving field. Very few other books deal with this highly pertinent subject matter, and as such, it is a must-have for anyone working in the field of heterogeneous catalysis.