Table Of ContentACS SYMPOSIUM SERIES 653
Transition Metal Sulfur
Chemistry
Biological and Industrial Significance
1
org w00
pubs.acs.6-0653.f
http://k-199 Edward I. Stiefel, EDITOR
2 | 1/b Exxon Research and Engineering Company
12
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21
ober 7, doi: 10. Kazuko Matsumoto, EDITOR
Oct6 |
n 99 Waseda University
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Developed from a symposium sponsored by the
1995 International Chemical Congress of Pacific Basin Societies
American Chemical Society, Washington, DC
In Transition Metal Sulfur Chemistry; Stiefel, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Library of Congress Cataloging-in-Publication Data
Transition metal sulfur chemistry: biological and industrial significance /
Edward I. Stiefel, editor, Kazuko Matsumoto, editor.
p. cm.—(ACS symposium series, ISSN 0097-6156; 653)
"Developed from a symposium sponsored by the 1995 International
Chemical Congress of Pacific Basin Societies, Honolulu, Hawaii,
December 17-22, 1995."
1 Includes bibliographical references and indexes.
pubs.acs.org 6-0653.fw00 I1S.B TNr a0n-s8it4o1n2 m-3e4ta7l6 s-u0l phur compounds—Congresses.
2 | http://1/bk-199 I(1II9I.9 . 5ISn:tt eHierfonenalto,i olEundlauwl, aHCrdah weI.ma, ii1ic)9a 4l 2ICV-o .n Sg.re erIsiIes.s o.M f aPtascuimfico tBoa, sKina zSuokcoie, t1ie9s4 9-
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2010 QD411.8.T73T7 1996
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52.141 ber 29, This book is printed on acid-free, recycled paper.
6.1em Copyright © 1996
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by 2ate: All Rights Reserved. The appearance of the code at the bottom of the first page of each
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PRINTED IN THE UNITED STATES OF AMERICA
In Transition Metal Sulfur Chemistry; Stiefel, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Advisory Board
ACS Symposium Series
Robert J. Alaimo Cynthia A. Maryanoff
Procter & Gamble Pharmaceuticals R. W. Johnson Pharmaceutical
Research Institute
Mark Arnold
University of Iowa Roger A. Minear
University of Illinois
1 David Baker at Urbana-Champaign
org w00 University of Tennessee
pubs.acs.6-0653.f APfirzienrd aCmen trBaol sRee search AOTm&kTar aBmell NLaablaomrataosriues
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00
21 George W. Roberts
ober 7, doi: 10. MChaermyE Edi.t CCaomsteplalnioyn North Carolina State University
Oct6 | John R. Shapley
n 99 Margaret A. Cavanaugh University of Illinois
o1
52.141 ber 29, National Science Foundation at Urbana-Champaign
1m Arthur B. Ellis Douglas A. Smith
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17.6Nov University of Wisconsin at Madison Concurrent Technologies Corporation
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Lawrence P. Klemann William C. Walker
Nabisco Foods Group DuPont
Douglas R. Lloyd Peter Willett
The University of Texas at Austin University of Sheffield (England)
In Transition Metal Sulfur Chemistry; Stiefel, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Foreword
IHE ACS SYMPOSIUM SERIES was first published in 1974 to
provide a mechanism for publishing symposia quickly in book
form. The purpose of this series is to publish comprehensive
books developed from symposia, which are usually "snapshots
in time" of the current research being done on a topic, plus
pubs.acs.org 6-0653.fw001 sspoarromype otBh sreeaefdvto i terhteawe ba lmp esa yapomteefrrp iscoa oslbin uoetmen pn -uttbhsba elsiie ssthdo er pbedivoc iao.e skwF q eiousdri cp tfkuholityrs u aarnpsed appesrooro nspcsr,oii bainttltee rina.s ec nst,es c tehtsoe
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Octo6 | d er^) of the symposium, who become the editor(s) of the book.
n 99 The authors then revise their papers according to the recom
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6.1em who check that all necessary revisions have been made.
17.6Nov As a rule, only original research papers and original re
by 2ate: view papers are included in the volumes. Verbatim reproduc
d D tions of previously published papers are not accepted.
nloadecation ACS BOOKS DEPARTMENT
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In Transition Metal Sulfur Chemistry; Stiefel, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Preface
ELEMENTAL SULFUR, "BRIMSTONE", and its basic chemistry were
known to the ancients. The simple sulfur anion, S~, is likely responsible
3
for the blue color of the ancient gemstone Lapis lazuli (lazurite). These
long-known features of sulfur chemistry illustrate some of the variety of
redox and aggregation states available to sulfur, even in the absence of a
transition metal ion.
g 01
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p://199 source of mercury. Molybdenite, molybdenum disulfide, now known to
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12
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21 implements (molybdos is the Greek word for pencil!). In more recent
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n Oct996 | als. For example, molybdenite is the source of metallic molybdenum,
2.141 oer 29, 1 wtiohnicsh. has major uses in steels, catalysts, lubricants, and other applica
15mb The ubiquity of transition metal sulfur compounds in nature has been
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ated. The exposition of this newly discovered chemistry, in juxtaposition
with industrial uses and biological manifestations, constitutes the main
theme of this volume.
The industrial uses of transition metal sulfur compounds are of great
current interest and economic importance. Various compounds are
important in lubrication, semiconductor applications, and catalysis.
Hydrotreating catalysis, that is, hydrodesulfurization, hydrodenitrogena-
tion, and hydrodemetallation, plays a major role in the processing of
petroleum. The commercial hydrotreating catalysts contain molybdenum
or tungsten sulfides promoted by cobalt or nickel, and much work has
been done on the catalysts themselves and on their putative model sys
tems.
ix
In Transition Metal Sulfur Chemistry; Stiefel, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Of more recent apprehension is the presence of transition metal sul
fur sites at many metalloprotein active centers. These sites are involved
with simple electron-transfer reactions and with such noteworthy chemi
cal reactions as oxygen atom transfer (on nitrogen and sulfur oxyanions
and heterocyclic molecules); activation of small molecules such as dinitro-
gen, dihydrogen, and dioxygen; structural recognition of DNA; and impor
tant biological metal-sensing, -processing, and -detoxification systems.
Seven of the 10 biologically essential transition metals use sulfur
coordination in some or all of their biological manifestations.
Iron-sulfur sites are biologically ubiquitous. All molybdenum and
tungsten enzymes use sulfur coordination in their respective Mo and W
cofactors. Many Cu, Ni, and Zn proteins have sulfur in their metal-
coordination spheres. Perhaps the most spectacular of the transition
bs.acs.org 0653.pr001 miarnoednt a-ltm heos ulylifbruodrne n-svuiatmens a pdfriououtmeni dnp roionft etnihnae tuonrfi ter tohagere ena -lfttihexrean tiaoutninv uees nunzayiltm rocegl ue(snntaeistrreso. goeXfn a-rtsaheye)
p://pu1996- crystallography has revealed structures that were not fully expected.
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12
2010 This volume presents a broad exposition of molecular transition metal
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n Oct996 | chemistry and are also of great value for the insights they provide con
o1 cerning industrial and biological systems.
2.141 er 29, The first chapter provides an overview of biological and industrial
15mb aspects of transition metal sulfur chemistry and highlights some of the key
66.ve trends that are emerging in the study of these systems. The chapters in
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cially, model molecular systems that react with the thiophenes and ben-
zothiophenes. The reactions studied in the molecular systems provide
food for thought concerning the functioning and, possibly, the improve
ment of industrial hydrotreating catalysts.
In chapters 12 through 18, the emphasis is on novel structures that, to
an increasing extent, are being prepared in high yields by systematic
approaches. The resultant clusters and complexes reveal intriguing struc
tural, electronic-structural, and reactivity properties and interesting
analogies to solid-state and enzymatic structures.
Chapters 19 through 21 show aspects of the reactivity of mononuclear
and polynuclear transition metal sulfur compounds. The chemistry is
diverse, involving metal-based as well as ligand-based reactions, which
have implications for both industrial and biological systems.
χ
In Transition Metal Sulfur Chemistry; Stiefel, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
By placing the molecular studies in the context of the enzymatic and
industrial catalytic systems, we hope that the collected contributions will
have a stimulatory effect on all of the areas discussed. This book should
be useful to those entering any of these exciting fieldsa nd to those seek
ing an overview of some of the fascinating work that is in progress world
wide.
This volume was developed from a symposium presented at the Inter
national Chemical Congress of Pacific Basin Societies in Honolulu,
Hawaii, in December 1995. Researchers at the frontiers of transition
metal sulfur chemistry from the Pacific Basin and from Europe have con
tributed to this book. The worldwide representation allows broad and
up-to-date coverage of this rapidly expanding area of chemistry.
g 01 Acknowledgments
s.acs.or653.pr0 We are grateful to Joyce Stoneking for her assistance in handling many of
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12
00 ganic Chemistry, Inc., the Esso Company (Japan), the Exxon Research
21
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Oct6 | assistance during the assembly and production of this volume.
n 99
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52.141 ber 29, EEDxxWoAn RRDe sIe. aSrcThIE FanELd Engineering Company
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Tokyo 169
Japan
September 3, 1996
xi
In Transition Metal Sulfur Chemistry; Stiefel, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Chapter 1
Transition Metal Sulfur Chemistry: Biological
and Industrial Significance and Key Trends
Edward I. Stiefel
Exxon Research and Engineering Company, Clinton Township,
Route 22 East, Annandale, NJ 08801
g 01
orh0 Transition metal sulfur (TMS) sites in biology comprise
s.acs.653.c mmoetnaollnoupcrloetaerin, s.a ndI nh oimndou-s trayn, dt hhee teursoep oloyfn uTclMeaSr scyesntetemrss iinn
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pu6- lubrication and in hydrotreating catalysis is of great technological
p://199 significance. Trends in the structure and reactivity of molecular
httk- TMS systems include: increasing nuclearity with higher d
2 | 1/b -electronic configuration; structural overlap of molecular and solid
0102 state systems; redox reactivity of ligand as well as metal sites;
21
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Oct6 | emphasized.
n 99
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2.141 er 29, The chemistry of the transition metals is exquisitely exploited in both biology and
5b
1m industry. In many of these applications, the transition metal is coordinated by sulfur,
6.e
6v either in the form of a sulfur-containing organic ligand or in the form of a variety of
17.No inorganic sulfur-donor groups. This book deals with the chemistry of the biological
by 2ate: and industrial systems, and, in large part, with related molecular systems. This
d D introductory chapter sets the background for the collected papers in this volume.
nloadecation From fFerirresdt,o txhines s,c polpaseto ocyf atrnainnssi,t ioannd m zientacl fsinuglfeurrs styos tceymtosch irnom bieo loPg4y50 i,s h dyidsrcougsesneads.e ,
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encompass seven different transition metals and with nuclearity (number of metal
centers) up to eight. In some cases, the role of sulfur involves the modulation of the
activity of the transition metal, but often the sulfur ligand itself is involved in
substrate binding, acid-base activity, or redox processes crucial to active-site
turnover. Much work in biomimetic chemistry is directed at duplicating, or at least
imitating, features of the metalloenzyme active-site structure, spectra, magnetism, and
reactivity.
The broad scope of transition metal sulfur species in industry also
encompasses a number of different metals. The industrial interest includes catalysis,
corrosion, lubrication, antioxidancy, and battery technology. Most, but not all, of the
activity is associated with solid state systems and heterogeneous catalysis. Molecular
species serve as precursors to the solid-state systems and, moreover, may have
0097-6156/96/0653-0002S19.25/0
© 1996 American Chemical Society
In Transition Metal Sulfur Chemistry; Stiefel, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
1. STIEFEL Transition Metal Sulfur Chemistry: Key Trends 3
H V VI
Β C Ν 0
Na Mg Yl Si Ρ s Cl
Κ Ca Co [NiJ [ZrJ Se Br
I
Figure 1. Bioinorganic Periodic Table highlighting those essential elements that
g 01 use sulfur coordination for some of their biological functions.
orh0
s.acs.653.c catalytic activity of their own or display chemical reactivity relevant to the study of
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p://199 In addition to the intrinsic interest in the novel chemistry of transition metal
httk- sulfur systems, the molecular systems that are the principal subject of this volume,
2 | 1/b clearly have relevance to our apprehension of the functioning of both the biological
12
00 and industrial systems. This opening chapter briefly introduces the biological and
21
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od illustrate these trends by referring to work from our own laboratory, to review
Oct6 | articles, and to particular chapters in this volume.
n 99
o1
2.141 er 29, Transition Metal Sulfur Systems in Biology
5b
1m The explosive growth of the field of bioinorganic chemistry is replete with the
66.ve publication of five new "text" books (1-5). A significant component of the interest in
17.No transition metal sulfur chemistry stems from the use of transition metal sulfur species
by 2ate: as reagents in biochemical, physiological, and pharmacological contexts and, more
d D so, from the presence of a variety of transition metal sulfur sites in proteins and
nloadecation beniozlyomgiecsa.l Tmhaec rmometoall-escuullfeu rb yc osemrpvoinnge nats aim (opra rtthse )c rkietiyc aplalyrt iomf pitosr atacntitv ere saicteti.v ity to the
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metals so involved, seven of them, highlighted in the figure, are found to have sulfur
coordination in many of their biological occurrences. In some cases, such as
molybdenum and tungsten enzymes, all known systems involve coordination with
sulfur ligands.
The transition metal sulfur sites that occur in metalloenzymes can be
classified into two types. The first are mononuclear sites with specific protein or
cofactor ligation. The second are polynuclear sites in which sulfur bridges bind
together two or more metals.
Mononuclear Sites: The simplest of the mononuclear systems are the rubredoxin
proteins (6-9). These small proteins (M « 6,000) are involved in electron transfer and
contain a single tetrahedrally coordinated iron site (Figure 2a). Four cysteine
thiolates from the protein side chains provide the ligation to the iron, which can be
either in the ferrous or ferric state. Despite the simplicity of the system, much control
is possible over the redox properties of the site. The tetrahedral coordination of Fe in
rubredoxin is illustrated in Figure 2a. In Chapter 2, Wedd and co-workers reveal the
In Transition Metal Sulfur Chemistry; Stiefel, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
