Table Of Content103
Structure and Bonding
Managing Editor:
D.M.P. Mingos
Editorial Board:
A.J. Bard. I.G. Dance. P. Day. J.A. Ibers • T. Kunitake
T.J. Meyer. H.W. Roesky-J.-P. Sauvage
A. Simon. F. Wudl
Springer
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Group 13 Chemistry I
Fundamental New
Developments
Volume Editors:
H.W. Roesky and D.A. Atwood
With contributions by
H. H6pfl, L. Mahalakshmi, P.P. Power,
S. Schulz, D. Stalke
~ Springer
The series Structure and Bonding publishes critical reviews on topics of research
concerned with chemical structure and bonding. The scope of the series spans the
entire Periodic Table. It focuses attention on new and developing areas of modern
structural and theoretical chemistry such as nanostructures, molecular electronics,
designed molecular solids, surfaces, metal dusters and supramolecular structures.
Physical and spectroscopic techniques used to determine, examine and model
structures fall within the purview of Structure and Bonding to the extent that the
focus is on the scientific results obtained and not on specialist information
concerning the techniques themselves. Issues associated with the development of
bonding models and generalizations that illuminate the reactivity pathways and
rates of chemical processes are also relevant.
As a rule, contributions are specially commissioned. The editors and publishers
will, however, always be pleased to receive suggestions and supplementary
information. Papers are accepted for Structure and Bonding in English.
In references Structure and Bonding is abbreviated Struct Bond
and is cited as a journal.
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Managing Editor Volume Editors
Professor D. Michael P. Mingos Professor Herbert W. Roesky
Principal Institut Fir Anorganische Chemie
St. Edmund Hall der Universit~it G6ttingen
Oxford OX1 4AR, UK Tammannstr. 4
E-mail: [email protected] 37077 G6ttingen, Germany
E-mail: hroeskyOgwdg.de
Professor Dr. David A. Atwood
Department of Chemistry
University of Kentucky
Lexington, Kentucky, 40506 0055, USA
E-mail: Datwood@pop. uky.edu
Editorial Board
Prof. Allen J. Bard Prof. Ian G. Dance
Department of Chemistry and Biochemistry Department of Inorganic and Nuclear Chemistry
University of Texas School of Chemistry
24th Street and Speedway University of New South Wales
Austin, Texas 78712, USA Sydney, NSW 2052, Australia
E-mail: [email protected] E-mail: [email protected]
Prof. Peter Day, FRS Prof. James A. Ibers
Director and Fullerian Professor of Chemistry Department of Chemistry
The Royal Institution of Great Britain North Western University
21 Albemarle Street 2145 Sheridan Road
London WIX 4BS, UK Evanston, Illinois 60208-3113, USA
E-mail: [email protected] E-mail: [email protected]
Prof. Toyohi Kunitake Prof. Thomas J. Meyer
Faculty of Engineering: Associate Laboratory Director for Strategic and
Department of Organic Synthesis Supporting Research
Kyushu University Los Alamos National Laboratory
Hakozaki 6-10-1, Higashi-ku PO Box 1663
Fukuoka 812, Japan Mail Stop A 127
E-mail: [email protected] Los Alamos, NM 87545, USA
E-mail: [email protected]
Prof. Jean-Pierre Sauvage
Prof. Herbert W. Roesky
Facult6 de Chimie Laboratoires de Chimie
Organo-Min6rale Institut fiir Anorganische Chemie
Universit~ Louis Pasteur der Universit~it GiSttingen
4, rue Blaise Pascal Tammannstra£e 4
67070 Strasbourg Cedex, France D-37077 G6ttingen, Germany
E-mail: [email protected] E-mail: [email protected]
Prof. Fred Wudl Prof. Arndt Simon
Department of Chemistry Max-Planck-Institut f/Jr
University of California Festk6rperforschung
LosAngeles, CA 90024-1569, USA Heisenbergstraige 1
E-mail: [email protected] 70569 Stuttgart, Germany
E-mail: [email protected]
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Preface
Over the last decade our view of chemistry has evolved substantially. Whereas
individual researchers previously focused on specific areas of chemistry, such
as inorganic, organic, etc. we now take a more holistic approach. Effective and
efficient research projects now incorporate whatever aspects of the chemistry
subdisciplines that are needed to complete the intended work.
The main group elements have always been used in this manner. Depending
on the use of the elements, the resulting work can be described under any
heading of chemistry. The group 13 elements have been special in this regard
due to the very unique characters of the constituent elements. Thus, there is a
dramatic change in the properties of the elements when proceeding through
the series, B, A1, Ga, In, T1. This difference is one of the main reasons why these
elements have seen, and continue to see, such widespread usage in such
disparate applications as organic synthesis, electronic and structural materials,
and catalysis, to name but a few.
The widespread use and applicability, however, can be directly attributed to
the deep understanding of the fundamental properties associated with these
elements and their attendant compounds. The fundamental research conduct-
ed with these elements forms the foundation upon which all applications and
utility are built. The present Structure and Bonding volume is part of a three-
part series focused on fundamental, biological, and applied aspects of the
group 13 elements. It will showcase four new areas of fundamental work that
will either grow in importance in the coming years, or provide new insight into
potentially new areas.
The first chapter, "Structure and Bonding in Boron-Containing Macrocycles
and Cages - Comparison to Related Structures with Other Elements Including
Organic Molecules" is authored by Herbert H6pfl. It details the rich structural
chemistry that can be orchestrated using boron as a "linker" between well-
chosen organic units. An impressive range of three-dimensional compounds
results from these systems. This chapter will be the seminal work in this area
for many years to come.
In the second chapter, Phil Power continues his remarkable and contin-
uously successful search for new main group metal multiple bonding. The
chapter is entitled: Multiple Bonding Between Heavier Group 13 Elements, and
covers the astounding new developments that have occurred in this area in
VIII Preface
only the last few years. Much of this work has resulted from Power's own
activities.
The vast majority of group 13 compounds are neutral. In contrast, charged
compounds, and in particular systematic studies of compounds incorporating
these elements are rare. Due to their relevance in catalysis some studies of
anionic compounds are known. Studies of cationic compounds, however, are
essentially nonexistent. This area will be addressed by L. Mahalakshmi and
D. Stalke in chapter 3 entitled: The R2M+ Group 13 OrganometaUic Fragment
Chelated by P-Centered Ligands. This may be, perhaps, the first review focused
exclusively on cationic group 13 compounds. While the chapter itself is
fundamental, the implications of the work in Lewis acid-based reactions is
very clear. This chapter is surely a signal for others to begin exploring this
unique and interesting area.
Group 13-15 element compounds are now fairly commonplace semicon-
ducting materials, usually incorporating phosphorus or arsenic. A great deal,
however, remains to be discovered in group 13 combinations with the heavier
group 15 congeners, Sb and Bi. Stephan Schulz is at the leading edge of this
new, very difficult, area of endeavor. His chapter, the fourth in this book,
"Synthesis, Structure and Reactivity of Group 13/15 Compounds Containing
the Heavier Elements of Group 15, Sb and Bi" clearly outlines the unique
nature of this chemistry, and provides a "road-map" for any other researchers
wishing to get into this area.
Although containing only four chapters, this book really represents the "tip
of the iceberg" for fundamental research in these areas. Utilizing the
information clearly disseminated in these pages, many other researchers can
build and improve upon their own fundamental and applied group 13 science.
lune 2002 H.W. Roesky
David A. At-wood
Contents
Structure and Bonding in Boron-Containing Macrocycles
and Cages - Comparison to Related Structures
with Other Elements Including Organic Molecules
H. H6pfl ..............................................
Multiple Bonding Between Heavier Group 13 Elements
P. P. Power ............................................ 57
The R2M+ Group 13 Organometallic Fragment Chelated
by P-Centered Ligands
L. Mahalakshmi, D. Stalke ................................. 85
Synthesis, Structure and Reactivity of Group 13/15 Compounds
Containing the Heavier Elements of Group 15, Sb and Bi
S. Schulz .............................................. 117
Author Index Volumes 101-103 ............................. 167
Subject Index .......................................... 169
