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INORGANIC SYNTHESES
Volume 35
.......
Board of Directors
THOMAS B. RAUCHFUSS, president University of Illinois at Urbana-Champaign
DIMITRI COUCOUVANIS University of Michigan
MARCETTAY. DARENSBOURG Texas A&M University
JOHN R. SHAPLEY University of Illinois at Urbana-Champaign
Secretary to the Corporation
STANTON CHING Connecticut College
Future Volumes
36 GREGORY S. GIROLAMI and ALFRED P. SATTELBERGER University of Illinois
at Urbana-Champaign and Argonne National Laboratory
37 PHILIP P. POWER University of California at Davis
International Associates
MARTIN A. BENNETT Australian National University
FAUSTO CALDERAZZO University of Pisa
M. L. H. GREEN Oxford University
JACK LEWIS Cambridge University
RENE POILBLANC University of Toulouse
HERBERT W. ROESKY University of Gottingen
WARREN R. ROPER University of Auckland
F. G. A. STONE Baylor University
JAN REEDIJK Leiden University
H. VAHRENKAMP University of Freiburg
AKIO YAMAMOTO Tokyo Institute of Technology
Editor-in-Chief
THOMAS B. RAUCHFUSS
University of Illinois at Urbana-Champaign
.................................................................
INORGANIC
SYNTHESES
Volume 35
Copyright � 2010 by John Wiley & Sons, Inc. All rights reserved
Published by John Wiley & Sons, Inc., Hoboken, New Jersey
Published simultaneously in Canada
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Library of Congress Catalog Number: 39:23015
ISBN 978-0471-68255-4
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
PREFACE
This volume presents procedures to compounds that illustrate the scope of modern
inorganic and organometallic synthesis. Following the tradition of Inorganic
Syntheses, emphasis has been placed on useful compounds and methods. Reflect-
ing my own interests, transition metal derivatives are featured.
The largest chapter concerns NacNac complexes. Such complexes represent
versatile platforms for a variety of transformations. The NacNac ligands have
many desirable features, not the least of which is the scope of their substituted
derivatives. The set of procedures was organized by three leaders in this area,
Professors Daniel J. Mindiola, Patrick L. Holland, and Timothy H. Warren. In
addition to their own contributions, they recruited other colleagues so that the
chapter consists of procedures for NacNac complexes of all metals from scandium
to zinc.
The remaining sections of the book reflect several areas of contemporary
activity. Routes are described to a selection of platinummetal reagents that straddle
the inorganic and organometallic domains, including some complexes that are of
interest in the area of solar energy research. A chapter highlights important
complexes from the area of bioorganometallic chemistry. We present an excellent
selection of electronically and stereochemically unusual ligands that are easily
prepared and adaptable to many metals, for example, the NHCs, bispidines, and
Kl€aui’s metalloligand. There is little question that metal-organic frameworks
(MOFs)will emerge as an important area of research and possibly applications.We
are fortunate to have detailed procedures for importantmembers of this new family
of molecule-based materials provided by the leading group in this area. As is our
tradition, the volume includes a series of procedures that do not neatly fit into any
category, such as salts of the remarkable radical [B12Me12]� and the hydrophilic
[B12(OH)12]2�. Finally, we include a collection of versatile classical coordination
and organometallic complexes.
Inorganic Syntheses has benefited from outstanding contributions from across
the globe, so I thank these authors and checkers first. Of the many people who
helped produce this volume, I wish to recognized my graduate and undergraduate
students, several ofwhom are listed as checkers.My colleaguesGregGirolami and
Scott Denmark were sources of advice and encouragement in this venture as they
have been throughout my career at Illinois. Finally, I wish to acknowledge the
previous editors of Inorganic Syntheses who have inspired me by their example.
v
The first chemistry monograph that I ever bought was Inorganic Syntheses,
Volume XIII, edited by F. A. Cotton.
I dedicate this volume to the memory of Alan M. Sargeson, a frequent
contributor to Inorganic Syntheses, inspired chemist, and gentleman.
THOMAS B. RAUCHFUSS
University of Illinois at Urbana-Champaign, Urbana, IL
vi Preface
CONTRIBUTORS
Debashis Adhikari, Department of Chemistry and Molecular Structure Center,
Indiana University, Bloomington, IN 47405
Enzo Alessio, Dipartimento di Scienze Chimiche, Universita di Trieste, 34127
Trieste, Italy
NicoleL.Armanasco,ChemistryM313, School ofBiomedical, Biomolecular and
Chemical Sciences, The University of Western Australia, Crawley, WA 6009,
Australia
YosraM.Badiei,Department of Chemistry, GeorgetownUniversity,Washington,
DC 20057-1227
Murray V. Baker, Chemistry M313, School of Biomedical, Biomolecular and
Chemical Sciences, The University of Western Australia, Crawley, WA 6009,
Australia
Alison G. Barnes, Chemistry M313, School of Biomedical, Biomolecular and
Chemical Sciences, The University of Western Australia, Crawley, WA 6009,
Australia
Stefan Bernhard, Department of Chemistry, Princeton University, Princeton, NJ
08544
Soledad Betanzos-Lara, Department of Chemistry, University of Warwick,
Coventry CV4 7AL, UK
Steven M. Bischof, The Scripps Energy Laboratories, The Scripps Research
Institute, Jupiter, FL 33458
Karen J. Blackmore, Department of Chemistry, University of California, Irvine,
CA 92697
Ioannis Bratsos,Dipartimento di Scienze Chimiche, Universita di Trieste, 34127
Trieste, Italy
David H. Brown, Chemistry M313, School of Biomedical, Biomolecular and
Chemical Sciences, The University of Western Australia, Crawley, WA 6009,
Australia
Gloria Sanchez Cabrera, Centro de Investigaciones Quımicas, Universidad
Autonoma del Estado de Hidalgo, Pachuca, Estado de Hidalgo 42184, Mexico
vii
Maria Caporali, Consiglio Nazionale delle Ricerche, Istituto di Chimica dei
CompostiOrganometallici (ICCOM-CNR),50019SestoFiorentino(Firenze), Italy
Chien-Hong Chen, School of Applied Chemistry, Chung Shan Medical Univer-
sity, Taichung, Taiwan
Anthony R. Chianese, Department of Chemistry, Yale University, New Haven,
CT, 06520-8107
Karen P. Chiang, Department of Chemistry, University of Rochester, Rochester,
NY 14627
Young Keun Chung,Department of Chemistry, Seoul National University, Seoul
151-742, Korea
Joshua R. Clayton, Department of Chemistry and Biochemistry, University of
Colorado, Boulder, CO 80309
Eric D. Cline, Department of Chemistry, Princeton University, Princeton, NJ
08544
Peter Comba, Anorganisch-Chemisches Institut, Universitat Heidelberg,
D-69120 Heidelberg, Germany
Timothy R. Cook, Department of Chemistry, Massachusetts Institute of Tech-
nology, Cambridge, MA 02139-4307
Ryan E. Cowley, Department of Chemistry, University of Rochester, Rochester,
NY 14627
Robert H. Crabtree,Department of Chemistry, Yale University, New Haven, CT
06520-8107
Keying Ding, Department of Chemistry, University of Rochester, Rochester, NY
14627
Anders Døssing,Department of Chemistry, University of Copenhagen, DK-2100
Copenhagen Ø, Denmark
Christos Douvris, Department of Chemistry and Biochemistry, University of
Colorado, Boulder, CO 80309
Daniel L. DuBois, Chemical and Materials Sciences Division, Pacific Northwest
National Laboratory, Richland, WA 99352
Mary Rakowski DuBois, Chemical and Materials Sciences Division, Pacific
Northwest National Laboratory, Richland, WA 99352
Lisa Dudek, Department of Chemistry and Biochemistry, University of
California, Los Angeles, CA 90095-1569
viii Contributors
ThomasR.Dugan,Department of Chemistry, University ofRochester, Rochester,
NY 14627
Celine Fellay, Institut des Sciences et Ingenierie Chimiques, Ecole Polytechnique
Federale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland
Matthew G. Fete, Department of Chemistry and Biochemistry, University of
Colorado, Boulder, CO 80309
Anne Mette Frey, Department of Chemistry, University of Copenhagen, DK-
2100 Copenhagen Ø, Denmark
Benjamin R. Garrett,Department of Chemistry, University of Illinois at Urbana-
Champaign, Urbana, IL 61801
Starla D. Glover, Department of Chemistry and Biochemistry, University of
California at San Diego, San Diego, CA 92093
John C. Goeltz, Department of Chemistry and Biochemistry, University of
California at San Diego, San Diego, CA 92093
Luca Gonsalvi, Consiglio Nazionale delle Ricerche, Istituto di Chimica dei
Composti Organometallici (ICCOM-CNR), 50019 Sesto Fiorentino (Firenze),
Italy
Abraha Habtemariam, Department of Chemistry, University of Warwick, Cov-
entry CV4 7AL, UK
James Hauk, Department of Chemistry and Biochemistry, University of
California at San Diego, San Diego, CA 92093
M. Frederick Hawthorne, International Institute of Nano and Molecular Medi-
cine, University of Missouri, Columbia, MO 65211
Paul G. Hayes, Department of Chemistry and Biochemistry, University of
Lethbridge, Lethbridge, Alberta, Canada T1K 3M4
Valerie J. Hesler, Chemistry M313, School of Biomedical, Biomolecular and
Chemical Sciences, The University of Western Australia, Crawley, WA 6009,
Australia
Alan F. Heyduk, Department of Chemistry, University of California, Irvine, CA
92697
YutakaHitomi,Department ofMolecular Chemistry andBiochemistry, Doshisha
University, Kyotanabe, Kyoto 610-0321, Japan
Patrick L. Holland, Department of Chemistry, University of Rochester,
Rochester, NY 14627
Contributors ix
Maik Jakob,Anorganisch-Chemisches Institut, Universitat Heidelberg, D-69120
Heidelberg, Germany
Satish S. Jalisatgi, International Institute of Nano and Molecular Medicine,
University of Missouri, Columbia, MO 65211
Yuuji Kajita, Department of Molecular Chemistry and Biochemistry, Doshisha
University, Kyotanabe, Kyoto 610-0321, Japan
Marion Kerscher, Anorganisch-Chemisches Institut, Universitat Heidelberg,
D-69120 Heidelberg, Germany
SangBokKim,Department ofChemistry, BrownUniversity, Providence, RI 02912
Benjamin T. King, Department of Chemistry and Biochemistry, University of
Colorado, Boulder, CO 80309
Yoshihisa Kishima, Department of Molecular Chemistry and Biochemistry,
Doshisha University, Kyotanabe, Kyoto 610-0321, Japan
Wolfgang Klaui, Lehrstuhl I: Bioanorganische Chemie und Katalyse, Heinrich-
Heine-Universitat Dusseldorf, 40225 Dusseldorf, Germany
Masahito Kodera, Department of Molecular Chemistry and Biochemistry,
Doshisha University, Kyotanabe, Kyoto 610-0321, Japan
Elzbieta Kogut, Department of Chemistry, Georgetown University, Washington,
DC 20057-1227
Clifford P. Kubiak, Department of Chemistry, University of California at San
Diego, San Diego, CA 61801
Peter C. Kunz, Lehrstuhl I: Bioanorganische Chemie und Katalyse, Heinrich-
Heine-Universitat Dusseldorf, 40225 Dusseldorf, Germany
Gabor Laurenczy, Institut des Sciences et Ingenierie Chimiques, Ecole Poly-
technique Federale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland
Mark W. Lee, Jr., International Institute of Nano and Molecular Medicine,
University of Missouri, Columbia, MO 65211
Christopher S. Letko,Department of Chemistry, University of Illinois at Urbana-
Champaign, Urbana, IL 61801
Chin Hin Leung, Department of Chemistry, Yale University, New Haven, CT
06520-8107
Wen-Feng Liaw, Department of Chemistry, National Tsing Hua University,
Hsinchu 30043, Taiwan
x Contributors
Simon Lotz, Department of Chemistry, University of Pretoria, Pretoria 0002,
South Africa
Leonard A.MacAdams,Department of Chemistry and Biochemistry, University
of Delaware, Newark, DE 19716
Amanda E. Mack, Department of Chemistry, University of Illinois at Urbana-
Champaign, Urbana, IL 61801
Neal D.McDaniel,Department of Chemistry, Princeton University, Princeton, NJ
08544
Marie M. Melzer, Department of Chemistry, Georgetown University, Washing-
ton, DC 20057-1227
JosefMichl,Department of Chemistry and Biochemistry, University of Colorado,
Boulder, CO 80309; Institute of Organic Chemistry and Biochemistry, Academy
of Sciences of the Czech Republic, 16610 Prague 6, Czech Republic
Daniel J. Mindiola, Department of Chemistry and Molecular Structure Center,
Indiana University, Bloomington, IN 47405
Tomoyuki Nakagawa, Department of Molecular Chemistry and Biochemistry,
Doshisha University, Kyotanabe, Kyoto 610-0321, Japan
Andy I. Nguyen, Department of Chemistry, University of California, Irvine, CA
92697
Daniel G. Nocera, Department of Chemistry, Massachusetts Institute of Tech-
nology, Cambridge, MA 02139-4307
Michael R. North, Chemistry M313, School of Biomedical, Biomolecular and
Chemical Sciences, The University of Western Australia, Crawley, WA 6009,
Australia
Yasuhiro Ohki, Department of Chemistry, Graduate School of Science, and
Research center for Materials science, Nagoya University, Nagoya 464-8602,
Japan
Shun Ohta,Department of Chemistry, Graduate School of Science, and Research
center for Materials science, Nagoya University, Nagoya 464-8602, Japan
RoyA.Periana,TheScripps EnergyLaboratories, TheScrippsResearch Institute,
Jupiter, FL 33458
Maurizio Peruzzini, Consiglio Nazionale delle Ricerche, Istituto di Chimica dei
Composti Organometallici (ICCOM-CNR), 50019 Sesto Fiorentino (Firenze),
Italy
Contributors xi
Warren E. Piers, Department of Chemistry, University of Calgary, Calgary,
Alberta, Canada T2N 1N4
Robert D. Pike, Department of Chemistry, College of William and Mary,
Williamsburg, VA 23187
Chuleeporn Puttnual,Department of Chemistry and Biochemistry, University of
Delaware, Newark, DE 19716
Udo Radius, Institut fur Anorganische Chemie der Universitat Wurzburg, 97074
Wurzburg, Germany
Thomas B. Rauchfuss, Department of Chemistry, University of Illinois at
Urbana-Champaign, Urbana, IL 61801
Herbert W. Roesky, Institut fur Anorganische Chemie, Universitat Gottingen,
D-37077 Gottingen, Germany
D. Ruckerbauer, Institute of Chemistry, Inorganic Department, Karl-Franzens-
University, 8010 Graz, Austria
Peter J. Sadler,Department of Chemistry, University ofWarwick, Coventry CV4
7AL, UK
Alexander V. Safronov, International Institute of Nano andMolecular Medicine,
University of Missouri, Columbia, MO 65211
Thomas Schaub, BASF SE, 67056 Ludwigshafen, Germany
Bryan D. Stubbert, Department of Chemistry, University of Rochester,
Rochester, NY 14627
Shouheng Sun, Department of Chemistry, Brown University, Providence, RI
02912
DwightA. Sweigart,Department of Chemistry, BrownUniversity, Providence, RI
02912
Yoshimitsu Tachi, Department of Molecular Chemistry and Biochemistry,
Doshisha University, Kyotanabe, Kyoto 610-0321, Japan
Kazuyuki Tatsumi, Department of Chemistry, Graduate School of Science, and
Research Center for Materials Science, Nagoya University, Nagoya 464-8602,
Japan
Thomas S. Teets, Department of Chemistry, Massachusetts Institute of Technol-
ogy, Cambridge, MA 02139-4307
Klaus H. Theopold, Department of Chemistry and Biochemistry, University of
Delaware, Newark, DE 19716
xii Contributors
Leonard L. Tinker, Department of Chemistry, Princeton University, Princeton,
NJ 08544
Ba L. Tran, Department of Chemistry and Molecular Structure Center, Indiana
University, Bloomington, IN 47405
David J. Tranchemontagne, Department of Chemistry and Biochemistry, Uni-
versity of California, Los Angeles, CA 90095-1569
Michal Valasek, Institute of Organic Chemistry and Biochemistry, Academy of
Sciences of the Czech Republic, 16610 Prague 6, Czech Republic
Matthew S. Varonka, Department of Chemistry, Georgetown University,
Washington, DC 20057-1227
Victoria Volkis, Department of Chemistry and Biochemistry, University of
Colorado, Boulder, CO 80309
AdelinaM. Voutchkova,Department of Chemistry, Yale University, NewHaven,
CT 06520-8107
Timothy H. Warren, Department of Chemistry, Georgetown University,
Washington, DC 20057-1227
J. W. Wielandt, Institute of Chemistry, Inorganic Department, Karl-Franzens-
University, 8010 Graz, Austria
Stefan Wiese, Department of Chemistry, Georgetown University, Washington,
DC 20057-1227
Omar M. Yaghi, Department of Chemistry and Biochemistry, University of
California, Los Angeles, CA 90095-1569
Fabrizio Zanobini, Consiglio Nazionale delle Ricerche, Istituto di Chimica dei
Composti Organometallici (ICCOM-CNR), 50019 Sesto Fiorentino (Firenze),
Italy
IlyaZharov,Department of Chemistry andBiochemistry, University of Colorado,
Boulder, CO 80309
Francisco J. Zuno-Cruz, Centro de Investigaciones Quımicas, Universidad
Autonoma del Estado de Hidalgo, Pachuca, Estado de Hidalgo 42184, Mexico
Contributors xiii
DEDICATION
This volume is dedicated to the memory of four eminent chemists who made
outstanding contributions to inorganic chemistry in general and to Inorganic
Syntheses in particular. We mourn their passing, but we celebrate their
achievements.
ROBERT W. PARRY (EDITOR-IN-CHIEF, VOLUME XII, 1970)
Bob was born on October 1, 1917 in Ogden, UT, and died on December 1, 2006 in
Salt Lake City, UT, at the age of 89, following a stroke. He received his B.S. degree
in soil chemistry fromUtah StateAgricultural College (nowUtah StateUniversity)
(1940), his M.S. degree in soil chemistry from Cornell University (1942), and his
Ph.D. in inorganic coordination chemistry under John C. Bailar, Jr. (Editor-in-
Chief, Inorganic Syntheses, Volume IV, 1953) from the University of Illinois
(1946). He served on the chemistry faculties of the University of Michigan
(1946–1969) and the University of Utah (Distinguished Professor of Chemistry,
1969–1997).
An extraordinary teacher, Bob coauthored the widely used high school text,
Chemistry: Experimental Foundations (1970), was senior author of Prentice-
Hall’s high school chemistry curriculum program (CHEM STUDY), and was
coeditor of Prentice-Hall’s paperback series, Foundations of General Chemistry.
He mentored more than 60 Ph.D. students and postdoctoral fellows. His honors
include first recipient of the ACS Award for Distinguished Service in Inorganic
Chemistry (1965), Manufacturing Chemists Award for Excellence in the Teaching
of College Chemistry (1972), ACS Award in Chemical Education (1977),
Alexander von Humboldt Senior U.S. Scientist Award (1980, 1983), first State
of Utah Governor’sMedal in Science and Technology (1987), honorary doctorates
from the Utah State University (1985) and the University of Utah (1997), and the
ACS’s highest honor, the Priestley Medal (1993).
Bob authored more than 150 publications, not only on the boron hydrides but
also on gallium, phosphines, and the thermodynamics of chelation. Long active in
the ACS, he served as President (1982), member of the Council for more than 45
years and of the Board of Directors (1973–1983), and Associate Editor of the
Journal of the American Chemical Society (1966–1968, 1971–1980), and a
member of its Editorial Board (1969–1980). He was the founding editor of
Inorganic Chemistry (1960–1964) and a member of its Editorial Board
(1962–1979) and President of Inorganic Syntheses, Inc. (1969–1972). One of the
early leaders of the Gordon Research Conferences, hewas a member (1965–1972)
xv
and Chairman (1967–1968) of the GRC Board of Trustees. He was Executive
Secretary, Chairman, and Councilor of the American Association for the Ad-
vancement of Science between 1980 and 1995, and he held offices in the
International Union of Pure and Applied Chemistry between 1965 and 1982.
FRANK ALBERT COTTON (EDITOR-IN-CHIEF, VOLUME XIII, 1973)
Al, one of the twentieth century’smost prolific, creative, and influential inorganic
chemists and chemical educators, was born on April 9, 1930 in Philadelphia, PA,
and died following a violent attack on February 20, 2007 in College Station, TX,
at the age of 76. He received his primary, secondary, and undergraduate education
in Philadelphia, enrolling in the Drexel Institute of Technology, intending to
major in chemical engineering. He switched to chemistry and received his B.S.
degree from Temple University (1951). He began graduate study at Harvard
University, where he joined the research group of future (1973) Nobel chemistry
laureate Geoffrey Wilkinson and worked on ferrocene and other metallocenes.
After receiving his Ph.D. (1955), he became an Instructor at the Massachusetts
Institute of Technology. In 1961, at the age of 3l, he became MIT’s youngest full
Professor.
As one of the small number of chemists credited with initiating the renaissance
of inorganic chemistry that began in the 1950s, Al researched metal carbonyls,
ligand field theory, organometallic compounds, phosphine oxide and sulfide
complexes, metal complexes with high coordination numbers, protein X-ray
crystallography, fluxional organometallic molecules, and application of such
physicochemical techniques as infrared and ultraviolet spectroscopies to transition
metal complexes. His synthesis and characterization of the [Re2Cl8]� (1964)
opened a new field of research in multiple metal-metal bonds, metal clusters, and
extended solids. He proposed the hapto (h) nomenclature to indicate the structures
of p-bonded hydrocarbon ligands.
In 1971, Al became Robert A. Welch Professor of Chemistry and shortly
thereafter W. T. Doherty-Welch Distinguished Professor of Chemistry at Texas
A&M University, where he worked on the synthesis and characterization of
compounds with multiple and/or single metal–metal bonds and other unusual
species. He and his 118 Ph.D. students and more than 150 postdoctoral fellows
from over 30 countries produced more than 1600 publications. He was an ardent
and articulate advocate of ‘‘curiosity-driven’’ basic research.
Al received many awards from American and foreign societies, including the
U.S. National Medal of Science (1982), Robert A. Welch Award (1994), and
Israel’s Wolf Prize (2000). His major ACS honors include the Award in Inorganic
Chemistry (first recipient, 1962), Award for Distinguished Service in the Ad-
vancement of Inorganic Chemistry (1974), Award in Organometallic Chemistry
(2001), F. Albert Cotton Medal for Excellence in Chemical Research (first
recipient, 1995), George C. Pimentel Award in Chemical Education (2005), and
xvi Dedication
the ACS’s highest award, the Priestley Medal (1998). The ACS’s F. Albert Cotton
Award in Synthetic Inorganic Chemistry bears his name. He also received 29
honorary doctorates from universities around the world.
Al was a prominent scientific educator and textbook author. His Advanced
Inorganic Chemistry, coauthoredwith GeoffWilkinson, became a standard text. It
underwent six editions (1962–1999), sold more than half a million copies, and was
translated into 15 foreign languages. From his lecture notes, he wrote Chemical
Applications of Group Theory (1963, 1971, 1990). His Chemistry—An Investiga-
tive Approach (1973, 1976) was intended for high schools, and hisBasic Inorganic
Chemistry (1976, 1987, 1995) was an entry-level text.
FRED BASOLO (EDITOR-IN-CHIEF, VOLUME XVI, 1976)
Fredwas born of Italian immigrant parents on February 11, 1920 in Coello, a small
coal mining town in southern Illinois, and died on February 27, 2007 in Skokie, IL,
at the age of 87. Until he attended school, he spoke the Piedmontese dialect,
understanding but speaking little English. The first Coello resident to attend
college, he earned his B.Ed, degree from Southern Illinois Normal School (now
Southern Illinois University) (1940), intending to teach high school. However, he
pursued graduate studies at the University of Illinois on platinum complexes under
John C. Bailar, Jr. (Editor-in-Chief, Inorganic Syntheses, Volume IV, 1953),
earning his M.S. (1942) and Ph.D. (1943) degrees. After 3 years of war-related
research at Rohm and Haas near Philadelphia, PA, he joined the faculty of
Northwestern University as Instructor. He rose through the ranks, becoming
Charles E. and Emma H. Morrison Professor of Chemistry (1980–1990). He
served as Chairman of the Chemistry Department (1969–1972).
Fred realized that thework on kinetics andmechanisms of substitution reactions
on carbon being investigated by organic chemists could be applied to inorganic
coordination compounds such as those of cobalt(III) and platinum(II). He con-
vinced his colleagueRalphG. Pearson to join him in such studies, and the two soon
became leaders in the field, and their monograph, Mechanisms of Inorganic
Reactions (1958, 1967), became a classic. Their postulation of a SN1CB mecha-
nism for the base hydrolysis of cobalt(III) complexes led to a controversy with
Christopher K. Ingold and Ronald S. Nyholm that was resolved in Basolo and
Pearson’s favor and garnered them and Northwestern University a global
reputation.
Fred maintained an international perspective, spending sabbatical leaves
with Jannik Bjerrum (1954–1955) and Vincenzo Caglioti (1961–1962). He
regarded Italy as a second home and was elected to the Accademia Nazionale
dei Lincei (1987), the world’s oldest scientific society. He coauthored Coordi-
nation Chemistry (1964, 1986) with former student Ronald C. Johnson.
Fred cofounded the Inorganic Gordon Research Conference, which continues
today.
Dedication xvii
In the ACS, Fred was elected Chairman of the Division of Inorganic Chemistry
(1970), a member of its Executive Committee, and President of the society (1983).
He received the following ACS honors—Award in Inorganic Chemistry (1964),
Award for Distinguished Service in the Advancement of Inorganic Chemistry
(1975), George C. Pimentel Award in Chemical Education (1993), and the
Priestley Medal, the society’s highest honor (2001).
ALAN G. MACDIARMID (EDITOR-IN-CHIEF, VOLUME XVII, 1977)
Alan was born onApril 14, 1927 inMasterton, NewZealand, and died on February
7, 2007 in Philadelphia, PA, after falling in his home. His youth was spent in
poverty (his father lost his job because of the Great Depression), and he left high
school at the age of 16 to help support the family. As a part-time student with a low-
paying ‘‘lab boy’’ (janitor) job in the Chemistry Department of Victoria University
College at Wellington, he earned his B.Sc. degree (1947) and then became a
demonstrator and worked as an assistant. His first publication (in Nature, 1949)
dealt with S4N4, a molecule that played a role in his later Nobel-winning research.
After graduating with a M.Sc. degree with first class honors (1951), Alan
received a Fulbright Fellowship that enabled him to study the rate of exchange in14C-tagged metal cyanide complexes at the University of Wisconsin, Madison,
from which he received his M.S. (1952) and Ph.D. (1953) degrees. With a New
Zealand Shell graduate scholarship, he then studied silicon hydrides underHarry J.
Emel�eus at Cambridge University, earning his second Ph.D. degree (1955).
Following short stints at Queen’s College and the University of St. Andrews, he
joined the Department of Chemistry at the University of Pennsylvania, where he
spent the remainder of his career, rising through the ranks and becomingBlanchard
Professor of Chemistry (1988). In 2002, he became James Von Ehr Distinguished
Professor of Science & Technology at the University of Texas, Dallas.
After devoting himself to silicon chemistry for two decades, Alan began a
fruitful collaborationwith his colleagueAlan J.Heeger on the conducting polymer,
(SN)x, the precursor to which he had studied in Wellington. While a Visiting
Professor at Kyoto University, Alan visited the Tokyo Institute of Technology,
where Hideki Shirakawa showed him a silvery film of polyacetylene. Shirakawa
accepted Alan’s invitation to spend a year with him studying this substance. They
discovered that the impurity in polyacetylene served as a dopant and increased its
conductivity. By adding bromine to the (CH)x films, they increased the conduc-
tivity by many millions of times. The two collaborated with Heeger, and in 2000
the trio shared theNobel Prize inChemistry ‘‘for the discovery and development of
conductive polymers.’’ Alan wrote more than 600 articles and held 20 patents. His
honors include the ACS’s Frederic Stanley Kipping Award in Silicon Chemistry
(1971) and Award in the Chemistry ofMaterials (1999); the RutherfordMedal, the
Royal Society of New Zealand’s highest honor (2000); election to the U.S.
NationalAcademyof Sciences (2002) and theOrder ofNewZealand, the country’s
xviii Dedication
highest honor (2002); and the fellowship in the Royal Society (2003). His alma
mater, Victoria University, awarded him an honorary doctorate (1999), created a
chair in physical chemistry in his name (2001), and named an Institute for
Advanced Materials and Nanotechnology after him (2003). Institutes named after
him include those at Jilin University in China (2001) and the University of Texas,
Dallas (2007).
STANLEY KIRSCHNER (EDITOR-IN-CHIEF, VOLUME XXIII, 1985)
Stan was born on December 17, 1927 in Brooklyn, New York and died on July 16,
2008. Stan attended New York City’s renowned Stuyvesant High School. He had
decided on a career in chemistry after his father, a pharmacist, presented himwith a
chemistry set when he was 11 years old.
After graduation Stan enlisted in the U.S. Navy (1944–1945), but then attended
Brooklyn College, from which he received his B.S. degree in 1950. Following a
brief stint with theMonsanto Chemical Company, he attendedHarvard University,
where hewon a departmental award as the best teaching fellow and fromwhich he
received his A.M. degree in 1952. He studied inorganic chemistry at theUniversity
of Illinois under John C. Bailar, Jr. (one of the founders of Inorganic Syntheses and
Editor-in-Chief of Volume 4, 1953). After receiving his Ph.D. in 1954, Stan joined
the faculty of Wayne State University in Detroit, Michigan, where he spent his
entire career, rising through the ranks and retiring as Professor Emeritus in 1992.
Stan was a longtime Secretary of the Editorial Board of Inorganic Syntheses.
His awards and honors include the Wayne State University President’s Award for
Excellence in Teaching (1969), Heyrovsk�y Medal of the Czechoslovak Academy
of Sciences (1978), the ACS Detroit Section’s Distinguished Service Award
(1980), the ChemicalManufacturers Award for Excellence in Chemistry Teaching
(1984), and the ACS Henry Hill Award and Engineering Society of Detroit’s Gold
Award (both in 1995),
Stan’s some one hundred articles dealt with the synthesis, structure, stereo-
chemistry, and biological properties of coordination compounds, including the
anticancer activity of platinum complexes; optical rotatory dispersion; circular
dichroism; the Pfeiffer Effect inmetal complexes; inorganic nomenclature; and the
application of computer techniques to chemical and information problems. A
prominent educator, he edited three books on inorganic and coordination
chemistry.
Because of his ebullient personality, organizational talent, and interest in
foreign languages, Stan held visiting professorships and similar honorary appoint-
ments across the globe. Among his many positions, he held positions at University
College, London (with Ronald S. Nyholm), University of S~ao Paolo in Brazil, theCentrul de Chimie in Timisoara and Institutul de Chimie in Cluj-Napoca in
Romania; the University of Florence, Tohoku University, and both the Technical
University and the University of Porto in Portugal. He held honorary membership
Dedication xix
in the national societies of most of these countries. Stan was an omnipresent
participant at the International Conference on Coordination Chemistry, the longest
running conference dedicated to inorganic chemistry. He attended every meeting
from 1959 to 2002 and serving as Permanent Secretary and Permanent Secretary
Emeritus.
GEORGE B. KAUFFMAN
California State University, Fresno, CA
xx Dedication
NOTICE TO CONTRIBUTORSAND CHECKERS
The Inorganic Syntheses series is published to provide all users of inorganic
substances with detailed and reliable procedures for the preparation of important
and timely compounds. Thus, the series is the concern of the entire scientific
community. The Editorial Board hopes that many chemists will share in the
responsibility of producing Inorganic Syntheses by offering their advice and
assistance in both the formulation and the laboratory evaluation of outstanding
syntheses. Help of this kind will be invaluable in achieving excellence and
pertinence to current scientific interests.
There is no rigid definition of what constitutes a suitable synthesis. The major
criterion by which syntheses are judged is the potential value to the scientific
community. An ideal synthesis is one that presents a new or revised experimental
procedure applicable to a variety of related compounds, at least one of which is
critically important in current research. Syntheses of individual compounds that
are of interest or importance are, however, also acceptable. Syntheses of com-
pounds that are readily available commercially at reasonable prices are ordinarily
not acceptable. Corrections and improvements of syntheses already appearing in
Inorganic Syntheses are suitable for inclusion.
The Editorial Board lists the following criteria of content for submitted
manuscripts. Style should conform with that of previous volumes of Inorganic
Syntheses. The introductory section should include a concise and critical summary
of the available procedures for synthesis of the product in question. It should also
include an estimate of the time required for the synthesis, an indication of the
importance and utility of the product, and an admonition if any potential hazards
are associated with the procedure. The Procedure section should present detailed
and unambiguous laboratory directions and bewritten so that it anticipates possible
mistakes and misunderstandings on the part of the person who attempts to
duplicate the procedure. Unusual equipment or procedure should be clearly
described. Line drawings should be included when they can be helpful. Safety
measures should be stated clearly. Sources of unusual starting materials must be
given, and, if possible, minimal standards of purity of reagents and solvents should
be stated. The scale should be reasonable for normal laboratory operation, and
problems involved in scaling the procedure either up or down should be discussed.
The criteria for judging the purity of the final product should be delineated clearly.
The Properties section should supply and discuss those physical and chemical
characteristics that are relevant to judging the purity of the product and to
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