The Rare Earth Elements: Fundamentals and Applications

Lanthanides [or Lanthanoids] are the elements with atomic numbers 57 to 71 on the Periodic Table. The sequential filling of their 4f electron shell gives them specific chemical and very unique spectroscopic properties.  These elements are actually not very rare at all, in earth s crust, but are usually found with many other elements. The absence or rarity of concentrated mineral deposits, in comparison to the more common metals, made them difficult to obtain pure in large quantities until specific mineral extraction technologies were developed. This has made the term rare earths less applicable in modern terms, and certainly does not accurately reflect the earth s abundance of these elements. Nevertheless, calling the lanthanides, rare earth elements has persisted and the name makes the lanthanides unique among the metals on the periodic chart, a uniqueness that is actually accurate, as this book will demonstrate

This book provides a comprehensive coverage of the basic chemistry, particularly inorganic chemistry, of the Rare Earth Elements. Inclusion of Group 3 elements (Sc, Y and La) and Group 13 elements (particularly Al) demonstrates how the Lanthanides relate to transition metals and main group elements in the Periodic Table. The book begins with chapters describing the fundamentals electronic, structural, and bonding trends of the elements to provide a foundation for understanding the specific chemistry described in subsequent chapters. The bulk of the chapters are organized based on the oxidation state of the elements, and particularly, the most common trivalent state. Within this organization the chapters focus on the wide variety of lanthanide compounds that form with specific types of ligands to provide a wide range of bonding environments. The book concludes with chapters describing the wide range of solid–state materials that contain, and utilize, lanthanides, followed by chapters on important, and newly–emerging, biological applications. The arrangement and content of the chapters in the book are designed to provide a fundamental understanding of lanthanide chemistry with examples of the most recent advances in research, and the important new and future applications of the Rare Earths.

Contributors xi

Series Preface xv

Volume Preface xvii

Geology, Geochemistry, and Natural Abundances of the Rare Earth Elements 1
Scott M. McLennan and Stuart Ross Taylor

Sustainability of Rare Earth Resources 21
David A. Atwood

The Electronic Structure of the Lanthanides 27
Ana de Bettencourt–Dias

Variable Valency 35
Andrew W. G. Platt

Group Trends 43
Andrew W. G. Platt

Solvento Complexes of the Lanthanide Ions 55
Simon A. Cotton and Jack M. Harrowfield

Lanthanides in Living Systems 65
Simon A. Cotton and Jack M. Harrowfield

Lanthanides: Coordination Chemistry 73
Simon A. Cotton and Jack M. Harrowfield

Organometallic Chemistry Fundamental Properties 83
Stephen T. Liddle

Lanthanides: Comparison to 3d Metals 105
Simon A. Cotton

Luminescence 111
Julien Andres and Anne–Sophie Chauvin

Lanthanides: Luminescence Applications 135
Julien Andres and Anne–Sophie Chauvin

Magnetism 153
Bing–Wu Wang and Song Gao

The Divalent State in Solid Rare Earth Metal Halides 161
Gerd Meyer

Lanthanide Halides 175
Timothy J. Boyle and Leigh Anna M. Steele

Lanthanide Oxide/Hydroxide Complexes 183
Zhiping Zheng

Lanthanide Alkoxides 197
Timothy J. Boyle and Leigh Anna M. Steele

Rare Earth Siloxides 205
Clemens Krempner and Brian McNerney

Thiolates, Selenolates, and Tellurolates 215
John G. Brennan

Carboxylate 225
Jia–sheng Lu and Ruiyao Wang

Lanthanide Complexes with Amino Acids 237
Zhiping Zheng

–Diketonate 249
Ke–Zhi Wang

Rare Earth Borides, Carbides and Nitrides 263
Takao Mori

Lanthanide Complexes with Multidentate Ligands 281
Xiaoping Yang, Richard A. Jones and Wai–Kwok Wong

Alkyl 299
Simon A. Cotton

Aryls 303
Simon A. Cotton

Trivalent Chemistry: Cyclopentadienyl 307
Roman A. Kresinski

Tetravalent Chemistry: Inorganic 313
Farid M. A. Sroor and Frank T. Edelmann

Tetravelent Chemistry: Organometallic 321
Farid M. A. Sroor and Frank T. Edelmann

Molecular Magnetic Materials 335
Bing–Wu Wang and Song Gao

Near–Infrared Materials 347
Lining Sun and Liyi Shi

Superconducting Materials 371
Antonio J. Dos santos–Garcia, Miguel Á. Alario–Franco and Regino Sáez–Puche

Metal–Organic Frameworks 385
John Hamilton Walrod II and David A. Atwood

Upconversion Nanoparticles for Bioimaging Applications 389
Jiefu Jin and Wing–Tak Wong

Oxide and Sulfide Nanomaterials 405
Takuya Tsuzuki

Rare Earth Metal Cluster Complexes 415
Gerd Meyer

Organic Synthesis 437
Yuichiro Mori and Sh Kobayashi

Homogeneous Catalysis 459
Yingming Yao and Kun Nie

Heterogeneous Catalysis 475
John Hamilton Walrod II and David A. Atwood

Supramolecular Chemistry: from Sensors and Imaging Agents to Functional Mononuclear and Polynuclear Self–Assembly Lanthanide Complexes 481
Jonathan A. Kitchen and Thorfinnur Gunnlaugsson

Endohedral Fullerenes 495
Daniel L. Burriss and David A. Atwood

Lanthanide Shift Reagents 501
Carlos F. G. C. Geraldes

Lanthanides: Magnetic Resonance Imaging 521
Sophie Laurent, Luce Vander Elst, Sebastien Boutry and Robert N. Muller

Luminescent Bioprobes 535
Anne–Sophie Chauvin

Sensors for Lanthanides and Actinides 561
Gabriela I. Vargas–Zúñiga and Jonathan L. Sessler

Index 575

In conclusion this is a valuable book, spanning the under–graduate / postgraduate divide, which should find a place particularly in the collections of those who teach lanthanide chemistry and new researchers to the field who want to discover the remarkable scope of modern lanthanide chemistry and its exciting applications. One could not expect much more in a single volume.   (Applied Organometal Chemistry, 1 May 2013)