The Rare Earth Elements

David Allan Atwood was born in 1965 in Urbana Illinois. At an early age David moved to Tuscaloosa Alabama where he grew up and ultimately attended college. After graduation from the University of Alabama he moved to Austin Texas to attend graduate school at the University of Texas with Richard Jones as his advisor. He graduated with his PhD (in Inorganic Chemistry) in the Spring of 1992 but stayed in Austin as a postdoctoral associate with Alan Cowley until his wife, Vicki Ossink Atwood, finished her PhD (also in Inorganic Chemistry). From UT he moved as an Assistant Professor to North Dakota State University as part of their new Center for Main Group Chemistry (of which he was co-director). In 1998 David Atwood joined the chemistry department at the University of Kentucky faculty as an Associate Professor. He now has over 160 publications, 10 patents, and serves on numerous editorial boards, including the Encyclopedia of Inorganic Chemistry, a 10 volume set published in Fall 2005. He is the founding editor and editor-in-chief of Main Group Chemistry. His research interests include detection and removal of heavy metal contaminants such as mercury, cadmium and lead, from the environment, the preparation of nanoparticulate metal oxides, prevention of aluminum alloy oxidation, and the synthesis of new Lewis acid compounds to effect new reactions, such as the breaking of phosphate esters bonds like those found in nerve gas agents and pesticides and the destruction of methyl-t-butyl ether (MTBE) a widespread water contaminant.

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

β-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 Shũ 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