Inorganic Chemistry in Focus III

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Edition: 1st
Format: Paperback
Pub. Date: 2006-09-11
Publisher(s): Wiley-VCH
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Summary

Metal clusters are on the brink between molecules and nanoparticles in size. With molecular, nano-scale, metallic as well as non-metallic aspects, metal clusters are a growing, interdisciplinary field with numerous potential applications in chemistry, catalysis, materials and nanotechnology.This third volume in the series of hot topics from inorganic chemistry covers all recent developments in the field of metal clusters, with some 20 contributions providing an in-depth view. The result is a unique perspective, illustrating all facets of this interdisciplinary area: Inter-electron Repulsion and Irregularities in the Chemistry of Transition Series Stereochemical Activity of Lone Pairs in Heavier Main Group Element Compounds How Close to Close Packing? Forty-Five Years of Praseodymium Diiodide Centered Zirconium Clusters Titanium Niobium Oxychlorides Trinuclear Molybdenum and Tungsten Cluster Chalcogenides Current State of (B,C,N)-Compounds of Calcium and Lanthanum Ternary Phases of Lithium with Main-Group and Late-Transition Metals Polar Intermetallics and Zintl Phases along the Zintl Border Rare Earth Zintl Phases Structure-Property Relationships in Intermetallics Ternary and Quaternary Niobium Arsenide Zintl Phases The Building Block Approach to Understanding Main-Group-Metal Complex Structures Cation-Deficient Quaternary Thiospinels A New Class of Hybrid Materials via Salt Inclusion Synthesis Layered Perrhenate and Vanadate Hybrid Solids Hydrogen Bonding in Metal Halides Syntheses and Catalytic Properties of Titanium Nitride Nanoparticles Solventless Thermolysis New Potential Scintillation Materials in Borophosphate Systems.With its didactical emphasis, this volume addresses a wide readership, such that both students and specialists will profit from the expert contributions.

Author Biography

Gerd Meyer studied chemistry at the Justus-Liebig University in Giessen under the supervision of Rudolf Hoppe. He gained his doctorate in 1976, and in 1980 worked with John D. Corbett at Iowa State University. In 1982 he gained his lecturing qualification in inorganic chemistry at Giessen, becoming a Full Professor at the University of Hanover in 1988. He subsequently moved to the same position at the University of Cologne in 1996. Professor Meyer's main research interests focus on solid-state and coordination chemistry of rare-earth elements and transition elements.<br> Dieter Naumann studied chemistry at the Rheinisch-Westfaelische Technische Hochschule (RWTH) at Aachen. His diploma (1967) and doctoral theses (1969) were supervised by Martin Schmeisser. Research on perfluoroalkyl iodine compounds led to his lecturing qualification in inorganic chemistry at the University of Dortmund in 1975. From 1967 until 1989 he was a professor in Dortmund, becoming a Full Professor of Inorganic and Analytical Chemistry at the University of Cologne in 1989. His main research interests are syntheses of fluoroorgano groups 10 to 18 element compounds.<br> Lars Wesemann studied chemistry at the Rheinisch-Westfaelische Technische Hochschule in Aachen. His diploma and doctoral theses were supervised by Gerhard E. Herberich, and he gained the latter in 1990. After that he worked in Dietmar Seyferth's group at MIT for one year before returning to the RWTH Aachen. Independent research led him to his lecturing qualification in inorganic chemistry in 1997. He was a Professor of Inorganic Chemistry at the University of Cologne from 1999 until 2003, and is now a Full Professor at the University of Tnbingen.

Table of Contents

Dedicated V
In Praise of Synthesis VII
Preface XIX
List of Contributors XXI
Biographical Sketches XXV
1 Inter-electron Repulsion and Irregularities in the Chemistry of Transition Series
1(14)
David A. Johnson
1.1 Introduction: Irregularities in Lanthanide Chemistry
1(3)
1.2 A General Principle of Lanthanide Chemistry
4(2)
1.3 Extensions of the First Part of the Principle
6(2)
1.4 Extensions of the Second Part of the Principle
8(1)
1.5 The Tetrad Effect
9(2)
1.6 The Diad Effect
11(2)
References
13(2)
2 Stereochemical Activity of Lone Pairs in Heavier Main-group Element Compounds
15(14)
Anja-Verena Mudring
2.1 Introduction
15(1)
2.2 When Does a Lone Pair of Electrons Become Stereochemically Active? — Observations
16(1)
2.3 Theoretical Concepts
17(8)
2.3.1 Molecular/Complex Compounds
18(2)
2.3.2 Solid Materials
20(5)
2.4 Conclusions
25(1)
Acknowledgments
26(1)
References
26(3)
3 How Close to Close Packing?
29(16)
Hideo Imoto
3.1 Introduction
29(1)
3.2 Essential Features of Close Packing
30(1)
3.3 Parameter Definitions
30(3)
3.4 Correlation Between D and N
33(2)
3.5 Transformation of Close-packing Arrangements
35(3)
3.6 Close-packing of Cations or of Anions?
38(3)
3.7 What Determines the Structure?
41(1)
Appendix. ICSD Codes, D and N Parameters of the Structures Used
42(2)
References
44(1)
4 Forty-five Years of Praseodymium Di-iodide, PrI2
45(16)
Gerd Meyer and Andriy Palasyuk
Foreword
45(1)
4.1 Introduction
46(1)
4.2 Phases and Structures in the System Praseodymium-Iodine
47(4)
4.2.1 Synthesis Generalities
47(1)
4.2.2 Structural Principles
48(3)
4.3 PrI2: Phases and Phase Analysis
51(7)
4.4 Conclusions
58(1)
Acknowledgments
59(1)
References
59(2)
5 Centered Zirconium Clusters: Mixed-halide Systems
61(18)
Martin Köckerling
Foreword
61(1)
5.1 The Basics of Zirconium Cluster Chemistry
61(1)
5.2 Motivation
62(1)
5.3 Mixed-Chloride-Iodide Zirconium Cluster Phases with a 6:12 Metal: Halide Ratio
63(1)
5.4 Mixed Chloride–Iodide Zirconium Cluster Phases with a 6:13 Metal: Halide Ratio
64(3)
5.5 Mixed Chloride–Iodide Zirconium Cluster Phases with a 6:14 Metal: Halide Ratio
67(4)
5.6 Mixed Chloride–Iodide Zirconium Cluster Phases with a 6:15 Metal: Halide Ratio
71(5)
5.7 Mixed Chloride–Iodide Zirconium Cluster Phases with a 6:18 Metal: Halide Ratio Products from Solid-state Reactions
76(1)
5.8 Outlook
77(1)
Acknowledgments
77(1)
References
77(2)
6 Titanium Niobium Oxychlorides: Ligand Combination Strategy for the Preparation of Low-dimensional Metal Cluster Materials
79(26)
Ekaterina V. Anokhina and Abdessadek Lachgar
Abstract
79(1)
6.1 Introduction
79(4)
6.1.1 Cluster Connectivity and Framework Dimension
81(1)
6.1.2 The Ligand Combination Approach to Creating Anisotropic Frameworks
82(1)
6.2 Overview of the Chemistry of Niobium Chloride and Niobium Oxide Cluster Compounds
83(2)
6.2.1 Synthesis and Chemical Properties
83(1)
6.2.2 Electronic Structure, Redox and Magnetic Properties
84(1)
6.3 Niobium Oxychloride Cluster Compounds
85(8)
6.3.1 One-dimensional Cluster Frameworks
85(1)
6.3.1.1 Frameworks Built from Clusters with Five Oxygen Ligands
85(1)
6.3.1.2 Frameworks Built of Clusters with Six Oxygen Ligands
86(2)
6.3.2 Two-dimensional Cluster Frameworks
88(1)
6.3.2.1 2D Oxychloride Frameworks with a Honeycomb-like Structure
88(1)
6.3.2.2 Pillared 2D Oxychloride Frameworks
90(1)
6.3.2.3 2D Framework with Graphite-like Cluster Connectivity
90(3)
6.4 Summary of Crystallographic Data on Titanium Niobium Oxychlorides
93(6)
6.4.1 Effect of the Total Number of Ligands
93(2)
6.4.2 Cluster Configuration
95(1)
6.4.2.1 Relationships Between Ligand Arrangement and Direct Inter-cluster Linkages
95(1)
6.4.2.2 Relationships Between the Ligand Arrangement and Inter-cluster Linkages via Counter-ions
96(1)
6.4.3 Anion Segregation
97(1)
6.4.4 Structure-determining Factors in the Absence of "Hard" Cations
97(2)
6.5 Electronic Configuration of Niobium Oxychloride Clusters
99(1)
6.6 Conclusion and Outlook
100(1)
References
101(4)
7 Trinuclear Molybdenum and Tungsten Cluster Chalcogenides: From Solid State to Molecular Materials
105(16)
Rosa Llusar and Cristian Vicent
7.1 Introduction
105(2)
7.2 Synthesis and Structure of Molecular M3Q4 and M3Q7 Cluster Complexes
107(8)
7.2.1 Solid-state Synthesis: Dimensional Reduction
108(1)
7.2.2 Solution Routes: Excision
109(3)
7.2.3 Ligand Exchange Reactions
112(1)
7.2.3.1 M3Q4 Cluster Complexes
112(1)
7.2.3.2 M3Q7 Cluster Complexes
113(2)
7.3 Trinuclear Clusters as Building Units
115(4)
7.3.1 Molecular Conductors Based on M3Q7 Cluster Complexes
115(2)
7.3.2 Formation of Supramolecular Adducts
117(2)
Acknowledgments
119(1)
References
119(2)
8 Current State on (B,C,N) Compounds of Calcium and Lanthanum
121(20)
H. Jürgen Meyer
8.1 Introduction
121(1)
8.2 Problems and Pitfalls of some Calcium Compounds with (mixed) B,C,N Anions
121(8)
8.2.1 Borides of Calcium and Lanthanum
123(1)
8.2.2 The CaC2 Problem and Ca3C12C3
124(2)
8.2.3 Calcium Nitride and Calcium Carbodiimides
126(1)
8.2.4 Calcium Nitridoborates
126(1)
8.2.5 A Comparison of Ca3(BN2)2 and Sr3(BN2)2 Structures
126(3)
8.3 Metal-nitridoborates
129(2)
8.3.1 Electronic Considerations
129(2)
8.4 Lanthanum Nitridoborates
131(6)
Compounds in Ca-B-N and La-B-N systems
132(1)
8.4.1 Nitridoborate Ions
133(1)
8.4.2 Structures of Lanthanum Nitridoborates
134(3)
8.5 Outlook
137(1)
Acknowledgments
138(1)
References
138(3)
9 Compositional, Structural and Bonding Variations in Ternary Phases of Lithium with Main-group and Late-transition Elements
141(16)
Claude H. Belin, Monique Tillard
9.1 Introduction
141(1)
9.2 Tuning Structures and Properties in Lithium Binary and Ternary Systems
142(1)
9.3 Clustering in Condensed Lithium Ternary Phases: A Way Towards Quasicrystals
143(1)
9.4 Exploration of New Lithium Ternary Systems Containing Ag, Zn, Al, Si, Ge
144(5)
9.4.1 Background
144(1)
9.4.2 The System Li-Al-Ag
145(1)
9.4.3 Compositional and Structural Variations in the System Li-Al-Si
146(2)
9.4.4 The Tetragonal Compound Li9AlSi3, a Good Anodic Material
148(1)
9.5 The Intermetallic Li-Zn-Ge System, from Electron-poor to Electron-rich Phases
149(5)
9.5.1 The Electron-poor Hexagonal Phase LiZnGe
149(1)
9.5.2 The True Cubic Configuration of the Compound Li2ZnGe
150(2)
9.5.3 The Li-rich Compound Li8Zn2Ge3 with an Open-layered Anionic Framework
152(2)
9.6 Concluding Remarks
154(1)
References
154(3)
10 Polar Intermetallics and Zintl Phases along the Zintl Border 157(16)
Arnold M. Guloy
10.1 "First comes the synthesis..."
157(1)
J.D. Corbett
10.2 What are Intermetallics?
157(3)
10.3 The Zintl-Klemm Concept
160(1)
10.4 "Electron-poor" Polar Intermetallics
161(1)
10.5 Intermetallic ft-Systems
162(6)
10.6 Some Final Remarks
168(1)
References
169(4)
11 Rare-earth Zintl Phases: Novel Magnetic and Electronic Properties 173(10)
Susan M. Kauzlarich and Jiong Jiang
11.1 Introduction
173(1)
11.2 Structure
174(3)
11.3 Resistivity
177(1)
11.4 Magnetic Properties
178(1)
11.5 Magnetoresistance
179(1)
11.6 Summary
180(1)
Acknowledgments
181(1)
References
181(2)
12 Understanding Structure-forming Factors and Theory-guided Exploration of Structure–Property Relationships in Intermetallics 183(12)
Dong-Kyun Seo, Li-Ming Wu and Sang-Hwan Kim
12.1 Introduction
183(1)
12.2 Mn14Al56+xGe3-x (x=0.00, 0.32, 0.61)
184(4)
12.3 La5-xCaxGe4 (x=3.37, 3.66, 3.82) and Ce5-xCaxGe4 (x=3.00, 3.20, 3.26)
188(3)
12.4 Concluding Remarks
191(1)
Acknowledgments
191(1)
References
192(3)
13 Ternary and Quaternary Niobium Arsenide Zintl Phases 195(14)
Franck Gascoin and Slavi C. Sevov
13.1 Introduction
195(2)
13.2 New Main-group Arsenides
197(2)
13.3 Compounds Based on Isolated [NbAs4] Tetrahedral Centers
199(5)
13.4 Compounds Based on Edge-sharing Dimers of [NbAs4] Tetrahedra
204(2)
References
206(3)
14 The Building-block Approach to Understanding Main-group-metal Complex Structures – More than just "Attempting to Hew Blocks with a Razor" 209(16)
Peter K. Dorhout
14.1 Introduction
209(1)
14.2 The Building-block Approach
210(11)
14.2.1 Quaternary Rare-earth Metal Chalcophosphates
210(3)
14.2.2 Quaternary Rare-earth Metal Chalcoarsenites and Antimonites
213(2)
14.2.3 Quaternary Rare-earth Metal Chalcotrielates and Tetrelates
215(6)
14.3 Summary
221(1)
References
222(3)
15 Cation-deficient Quaternary Thiospinels 225(14)
Ashok K. Ganguli, Shalabh Gupta and Gunjan Garg
15.1 Introduction
225(2)
15.2 Cu5.5Si 1.5Fe4Sn12S32
227(6)
15.3 Cu5.47Fe2.9Sni3.1532
233(2)
15.4 Cu7.38Mn4Sn12S32 (1) and Cu7.07Ni4Sn12S32 (2)
235(1)
15.5 Conclusions
236(1)
References
236(3)
16 A New Class of Hybrid Materials via Salt-inclusion Synthesis 239(12)
Shiou-Jyh Hwu
16.1 Introduction
239(2)
16.2 General Approach to Salt-inclusion Synthesis
241(1)
16.3 Examples and Discussion
242(6)
16.3.1 Zeolite-like Transition Metal Containing Porous Compounds
242(2)
16.3.2 Non-centrosymmetric Solids (NCSs)
244(3)
16.3.3 Solids Containing Periodic Arrays of Transition-metal Nanostructures
247(1)
16.4 Final Remarks
248(1)
Acknowledgments
249(1)
References
249(2)
17 Layered Perrhenate and Vanadate Hybrid Solids: On the Utility of Structural Relationships 251(16)
Paul A. Maggard and Bangbo Yan
17.1 Introduction
251(1)
17.2 Heterometallic Perrhenates
252(7)
17.2.1 Background: Molecular and Condensed Metal-perrhenates
252(1)
17.2.2 Copper- and Silver-perrhenate Hybrids
253(3)
17.2.3 Metal-coordinated Pillars in Perrhenate Hybrids
256(3)
17.3 Heterometallic Vanadates
259(6)
17.3.1 Background: Layered Vanadate Species
259(2)
17.3.2 Layered Heterometallic Vanadates: Charge Density Matching
261(1)
17.3.3 Heterometallic Reduced Layered Vanadates
262(3)
17.4 Conclusions 265 Acknowledgments
265(1)
References
265(2)
18 Hydrogen Bonding in Metal Halides: Lattice Effects and Electronic Distortions 267(12)
James D. Martin
18.1 Introduction
267(1)
18.2 A Hierarchy of Structure-directing Forces
268(1)
18.3 Hydrogen Bond Influence on Melts and Crystallization
269(3)
18.4 Electronic Implications of Hydrogen Bonding
272(3)
18.5 Conclusions
275(1)
Acknowledgments
276(1)
References
276(3)
19 Syntheses and Catalytic Properties of Titanium Nitride Nanoparticles 279(16)
Stefan Kaskel
19.1 Introduction
279(1)
19.2 Synthesis of TiN Nanoparticles
280(5)
19.3 Titanium Nitride Nanoparticles in Hydrogen Storage Applications
285(3)
19.4 Catalytic Properties of TiN Nanoparticles in Solution
288(1)
19.5 Catalytic Properties
289(3)
References
292(3)
20 Solventless Thermolysis: A Possible Bridge Between Crystal Structure and Nanosynthesis? 295(10)
Ling Chen and Li-Ming Wu
20.1 Introduction
295(1)
20.2 Synthesis Methods
295(1)
20.3 Solventless Thermolysis and Some Examples
296(3)
20.3.1 Cu2S Nanodisks
297(1)
20.3.2 NiS Nanorods and Nanotrigonal Prisms
297(1)
20.3.3 Bi2S3 Nanowires, Rods and Fabric
298(1)
20.3.4 Pb3O2Cl2 Nanobelts
298(1)
20.4 Control of the Nanoproduct Morphology Through the State of the Precursor
299(1)
20.5 Crystal Structure of the Precursor versus the Morphology and Distribution of the As-synthesized Nanoproduct: A Possible Bridge Between these Two?
300(2)
20.6 Conclusion and Prospects
302(1)
Acknowledgment
302(1)
References
303(2)
21 New Potential Scintillation Materials in Borophosphate Systems 305(20)
Jing-Tai Zhao and Cheng-Jun Duan
21.1 Introduction
305(1)
21.2 Recent Studies on the Scintillation Luminescence Properties of Borophosphates
306(16)
21.2.1 The Crystal Structures of Ba3BP3O12, BaBPO5 and Ba3BPO7
306(2)
21.2.2 The Preparation and X-ray-excited Intrinsic Scintillation Luminescence Properties of Ba3BP3O12, BaBPO5 and Ba3BPO7
308(8)
21.2.3 The X-ray-excited Luminescence Properties of Ce3+ -activated Ba3BP3O12, BaBPO5 and Ba3BPO7
316(2)
21.2.4 Potential Scintillation Material of Ba3BP3O12: Eu²+
318(4)
21.3 Outlook
322(1)
References
323(2)
Subject Index 325

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