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Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, Selenium and Tellurium Volume 2 - Hardcover

 
9781849736244: Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, Selenium and Tellurium Volume 2

Inhaltsangabe

The Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, Selenium and Tellurium provides an overview of recent developments, particularly from the last decade, on the chemistry of the chalcogen group elements (S, Se and Te). While up to a few decades ago, chalcogen chemistry was mainly centred on sulphur, in recent years the research based on Se and Te has increased dramatically, and has created huge scope for the use of compounds based on this type of chemistry. The Handbook is organised into two parts, the first of which deals systematically with the chemistry of chalcogens in relation to other group elements in the periodic table. It also includes an overview of metal-chalcogenides and metal-polychalcogenides. The second part reflects the interdisciplinary nature of chalcogen chemistry and focuses on biological, materials and supramolecular aspects of the field. This Handbook gives a comprehensive overview on recent developments over the last decade and is ideal for researchers in the field.

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The Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, Selenium and Tellurium provides an overview of recent developments, particularly from the last decade, on the chemistry of the chalcogen group elements (S, Se and Te). While up to a few decades ago, chalcogen chemistry was mainly centred on sulphur, in recent years the research based on Se and Te has increased dramatically, and has created huge scope for the use of compounds based on this type of chemistry. The Handbook is organised into two parts, the first of which deals systematically with the chemistry of chalcogens in relation to other group elements in the periodic table. It also includes an overview of metal-chalcogenides and metal-polychalcogenides. The second part reflects the interdisciplinary nature of chalcogen chemistry and focuses on biological, materials and supramolecular aspects of the field. This Handbook gives a comprehensive overview on recent developments over the last decade and is ideal for researchers in the field.

Aus dem Klappentext

The Handbook of Chalcogen Chemistry: New Perspectives in Sulfur, Selenium and Tellurium provides an overview of recent developments, particularly from the last decade, on the chemistry of the chalcogen group elements (S, Se and Te). While up to a few decades ago, chalcogen chemistry was mainly centred on sulphur, in recent years the research based on Se and Te has increased dramatically, and has created huge scope for the use of compounds based on this type of chemistry. The Handbook is organised into two parts, the first of which deals systematically with the chemistry of chalcogens in relation to other group elements in the periodic table. It also includes an overview of metal-chalcogenides and metal-polychalcogenides. The second part reflects the interdisciplinary nature of chalcogen chemistry and focuses on biological, materials and supramolecular aspects of the field. This Handbook gives a comprehensive overview on recent developments over the last decade and is ideal for researchers in the field.

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Handbook of Chalcogen Chemistry Volume 2

New Perspectives in Sulfur, Selenium and Tellurium

By Francesco Antonio Devillanova, Wolf-Walther du Mont

The Royal Society of Chemistry

Copyright © 2013 The Royal Society of Chemistry
All rights reserved.
ISBN: 978-1-84973-624-4

Contents

Introduction F. A. Devillanova and W.-W. duMont, 1,
Volume 1,
Chapter 1 Compounds Containing Boron–Chalcogen Bonds Michael A. Beckett, 5,
Compounds Containing the Carbon-Chalcogen Bond (E = S, Se, Te),
Chapter 2.1 Thiolates, Selenolates, and Tellurolates M. Concepción Gimeno, 37,
Chapter 2.2 Thioamides, Thioureas, and Related Selenium and Tellurium Compounds Mamoru Koketsu, 94,
Chapter 2.3 Chalcogenone C=E Compound (E=S, Se, Te) Gaetano Verani and Alessandra Garau, 118,
Chapter 3 Compounds Having Both a Single Bond and a Double Bond (Heavy Ketones) between Si, Ge, or Sn and Chalcogens (S, Se, and Te) Nobuhiro Takeda and Norihiro Tokitoh, 160,
Chapter 4 Recent Developments in Chalcogen–Nitrogen Chemistry Tristram Chivers and Risto Laitinen, 191,
Chapter 5 Chalcogen–Phosphorus (and Heavier Congener) Compounds Rob Davies and Laura Patel, 238,
Chapter 6 Compounds Containing the Chalcogen Oxygen E–O Bond (E=S, Se, Te) Mathias S. Wickleder and Christian Logemann, 307,
Compounds Containing the Chalcogen–Chalcogen E–E Bond (E=S, Se, Te),
Chapter 7.1 Structure and Bonding of the Neutral Chalcogens and Their Polyatomic Cations Ingo Krossing, 349,
Chapter 7.2 Organochalcogen Multication Species Valentine G. Nenajdenko, Nikolay E. Shevchenko, Elizabeth S. Balenkova and Igor V. Alabugin, 382,
Compounds Containing the Halogen–Chalcogen X–E Bond (X=F, Cl, Br, I; E=S, Se, Te),
Chapter 8.1 Recent Developments in Binary Halogen–Chalcogen Compounds, Polyanions, and Polycations Jing Wang and Zhengtao Xu, 425,
Chapter 8.2 Charge-Transfer Adducts and Related Compounds Vito Lippolis and Francesco Isaia, 448,
Metal Chalcogenides,
Chapter 9.1 Metal Chalcogenides: Clusters, Layers, Nanotubes Maxim N. Sokolov, 475,
Chapter 9.2 Polychalcogenides William S. Sheldrick, 514,
Subject Index, 546,
Volume 2,
Introduction F. A. Devillanova and W.-W. duMont, 1,
Biological Chemistry,
Chapter 10.1 Metal–Sulfur Clusters as the Model for the Active Sites of Metalloenzymes Yasushi Mizobe and Hidetake Seino, 7,
Chapter 10.2 Current Research on Mimics and Models of Selenium-Containing Antioxidants Bhaskar J. Bhuyan, Devappa S. Lamani, Govindasamy Mugesh and Thomas Wirth, 25,
Chapter 10.3 The Role of Sulfur and Selenium Species in the Thyroid Surendar Reddy Jakka and Govindasamy Mugesh, 47,
Material Chemistry,
Chapter 11.1 Stable Chalcogen Radicals Jeremy M. Rawson and John J. Hayward, 69,
Chapter 11.2 Chalcogen-Rich Compounds as Electron Donors Diego Cortizo-Lacalle, Peter J. Skabara and Thomas D. Westgate, 99,
Chapter 11.3 1,2-Dichalcogenolene Ligands and Related Metal Complexes Massimiliano Arca, M. Carla Aragoni and Anna Pintus, 127,
Chapter 11.4 II–VI Semiconductors and Their Device Applications Bin He and Wenjun Zhang, 180,
Chapter 11.5 Nanoparticles and Quantum Dots Lihui Yuwen and Lianhui Wang, 232,
Miscellaneous Aspects,
Chapter 12.1 Supramolecular Structures Based on Chalcogen–Halogen Secondary Bonds Wolf-Walther du Mont and Cristian George Hrib, 273,
Chapter 12.2 Synthesis and Stereochemistry of Optically Active Chalcogen Compounds Toshio Shimizu, 317,
Chapter 12.3 Hypervalent Chalcogen Compounds Satoko Hayashi and Waro Nakanishi, 335,
Chapter 12.4 Theoretical Calculations and NMR Spectroscopy Waro Nakanishi and Satoko Hayashi, 373,
Subject Index, 433,


CHAPTER 1

Metal–Sulfur Clusters as the Model for the Active Sites of Metalloenzymes

YASUSHI MIZOBE AND HIDETAKE SEINO

Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan


10.1.1 Introduction

Nitrogen is one of the essential elements for all living things and a significant part of the nitrogen needed on Earth is supplied in the form of ammonia produce from atmospheric nitrogen by biological nitrogen fixation. This highly important reaction, converting a quite inert N2 molecule into ammonia through coupled protonation and electronation, is known to proceed under ambient conditions by the catalysis of the metalloenzyme nitrogenase. This presents a sharp contrast to industrial nitrogen fixation, i.e. the Haber–Bosch process, which requires an extremely drastic condition to produce ammonia from gaseous nitrogen and hydrogen in the presence of an Fe-based heterogeneous catalyst. From the 1970s, certain Mo–Fe–S aggregates had been proposed as the active site structure of nitrogenase mainly on the basis of EXAFS data. It was in 1992 that the first report appeared about the results of the single-crystal X-ray diffraction study (2.7 Å resolution) for the most common nitrogenase, viz. Mo nitrogenase, which disclosed the surprising MoFe7S9 mixed-metal sulfido core present at the active site. From higher-resolution (1.16 Å) crystallographic results of in 2002, one light atom X (C, N, or O) was found to be at the centre of this core, as depicted in Figure 10.1.1. Although nitrogen was proposed to be most probable for the interstitial atom X at that time, it was characterized as carbon in more recent studies (2011) by using crystal structure at the stage of more accurate resolution (1.0 Å) and X-ray emission spectroscopy.

Owing to the remarkable progress in single-crystal X-ray analysis techniques, detailed structures have recently been clarified for a number of enzymes, which include several metalloenzymes containing the cluster cores with sulfur-bridged multimetallic centres at their active sites such as hydrogenase, sulfite reductase, and carbon monoxide hydrogenase/acetyl-CoA synthase (Figure 10.1.2), as well as nitrogenase. It is likely that the high catalytic activities of these enzymes result from the cooperation of two or more metal centres in proximity, making sulfur ligands such as sulfides and thiolates the choice as the bridges to maintain these multimetallic cores intact during catalysis. This is presumably because of the characteristics of the S atom, i.e. its strong affinity with transition metals and high bridging ability. However, although X-ray crystallographic analyses have successfully disclosed the active site structures of these enzymes in the resting state, the structures during catalytic turnover may possibly be different. Furthermore, their function mechanisms are essentially unknown. It is difficult to observe directly what is occurring at active sites embedded within huge proteins, so studies to synthesize model compounds and clarify their reactivity are of much importance. In this chapter, recent advances in the chemistry of metal–sulfur clusters as synthetic analogues to natural enzymes are briefly summarized.


10.1.2 Metal–Sulfur Clusters in Metalloenzymes and Syntheses of Their Structural Models

Iron–sulfur proteins are ubiquitous in all life forms, and at their active sites they most commonly contain the Fe2S2, Fe3S4, and Fe4S4 cluster cores shown in Figure 10.1.3 to mediate the electron transfer as their predominant role. In the early 1970s a synthetic approach to these iron–sulfur cluster sites was...

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