Table Of ContentACS SYMPOSIUM SERIES 917
Modern Aspects of Main
Group Chemistry
acs.org 7.fw001 Michael Lattman, Editor
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American Chemical Society, Washington, DC
In Modern Aspects of Main Group Chemistry; Lattman, M., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
Library of Congress Cataloging-in-Publication Data
Modern aspects of main group chemistry / Michael Lattman, editor ; Richard A. Kemp,
editor ; sponsored by the ACS Division of Inorganic Chemistry, Inc.
p. cm. — (ACS symposium series ; 917)
"Developed from a symposium sponsored by the Division of Inorganic Chemistry,
Inc. at the 227th National Meeting of the American Chemical Society, Anaheim,
California, March 28-April 1, 2004"—Pref.
Includes bibliographical references and index.
ISBN-13: 978-0-8412-3926-5 (alk. paper)
bs.acs.org 917.fw001 I1. .A Cmheermicaisntr yC,h eImnoircgaaln Sico—cieCtyo.n Dgrievsisseiso.n of Inorganic Chemistry, Inc. II. American
2, 2009 | http://pu0.1021/bk-2005-0 CQ54hD6e—1m5id1cc.a32l. M2S o6c3ie ty2. 0M0e5e ting (227th : 2004 : Anaheim, Calif.). III. Se2ri0e0s5. 048310
21 The paper used in this publication meets the minimum requirements of American
October 05 | doi: NMaattieorniaalls S, AtaNndSaIr Zd 3f9o.r4 8In-1fo9r8m4a.t ion Sciences—Permanence of Paper for Printed Library
6 on 1, 20 Copyright © 2006 American Chemical Society
4.13ber Distributed by Oxford University Press
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PRINTED IN THE UNITED STATES OF AMERICA
In Modern Aspects of Main Group Chemistry; Lattman, M., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
Dedication
acs.org 7.fw001
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wnlblic Professor Alan H. Cowley,
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The University of Texas, Austin
The organizers and participants wish to dedicate this volume to
Professor Alan H. Cowley on the occasion of his 70th birthday and
in honor of his many contributions to main group chemistry.
In Modern Aspects of Main Group Chemistry; Lattman, M., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
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In Modern Aspects of Main Group Chemistry; Lattman, M., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
Foreword
The ACS Symposium Series was first published in 1974 to pro
vide a mechanism for publishing symposia quickly in book form. The
purpose of the series is to publish timely, comprehensive books devel
oped from ACS sponsored symposia based on current scientific re
search. Occasionally, books are developed from symposia sponsored by
acs.org 7.fw001 aotuhdeiern ocreg.a nizations when the topic is of keen interest to the chemistry
bs.91 Before agreeing to publish a book, the proposed table of con
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October 05 | doi: manuscrAipst sa a rruel ep,r eopnalrye dor iing icnaaml errease-raeracdhy p faoprmerast .a nd original review
6 on 1, 20 papers are included in the volumes. Verbatim reproductions of previ
4.13ber ously published papers are not accepted.
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In Modern Aspects of Main Group Chemistry; Lattman, M., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
Preface
This volume is based on a symposium entitled Modern Aspects of
Main Group Chemistry, held at the 227th National Meeting of the
American Chemical Society (ACS) in Anaheim, California, March
28-April 1, 2004. Our goal was to bring together many of the well-
established leaders in the field of main group chemistry with several of
the "up-and-coming" younger scientists. As the invitation to participate
org 001 in the symposium was based only on the very broad topic of main group
acs.7.pr chemistry, this book reflects the diversity and richness in creativity that
2, 2009 | http://pubs.0.1021/bk-2005-091 chlgeuaraosrdr ueIibpnnne gtecal nhydp e drdPmaietrcifiotoisifntnterei syotsos,n o tetthrhhr iesesA booslacrrfnag ime naHnncathieiizn freiib ncrges rirr neoth oauaCsrpdgoo ancwanshnl ioeefcomty hcr, ei hshFret o.rmRmysti .oisSdntt.urig,v yr wiae. n hsignyo tm mhisepi notphdsae.i u sORtm n4o oe0b n eo yrmft e taAahire.ns
21
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136 on er 1, 20 dcoecnitdriebdu tthioants t htoe rien worogualndi cb ec hneom misotrrey athpapnro tpor ioatreg amniaznen ethr isto s ryemcopgonsiizuem h iins
34.mb his honor. Dubbed "CowleyFest 2004" by the participants, the symposi
y 89.163.ate: Dece usmma sllu cucneisvsefrusliltyie bs rtoou gthhet twogoertlhde'sr lsecaiednintigs tisn fsrtoitmut iaornosu, nwd itthhe t hweo rclodm, fmroomn
oaded bation D rthesepmeects bfoeri nPgr oofuers sinotre rCeostws leiny .m ain group chemistry and our affection and
wnlblic As the end product of the meeting, this book is targeted to academic
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to main group chemistry, including nanotechnology and polymer chem
istry, as well as to industrial chemists who want to become familiar with
main group chemistry in a minimum of time. In addition, we believe this
book will be a valuable resource for postdoctoral students, graduate
students, and advanced undergraduates who are conducting research in
main group chemistry. This book is designed to be used as a textbook or
reference book in a graduate level main group topics course as well.
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In Modern Aspects of Main Group Chemistry; Lattman, M., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
We are very grateful to all of the participants in this symposium,
many of whom took part while paying their own travel expenses. Additi
onally, we are particularly grateful to those participants who contributed
chapters to this book. The assortment of topics presented in this volume
is a testament to the importance of main group chemistry in the areas of
science and technology.
Financial support for this symposium came from a variety of sources.
A type SE Grant from the Petroleum Research Fund, administered by the
ACS, was instrumental in allowing several of the foreign speakers to
attend. Significant financial contributions from the following sources are
gratefully acknowledged as well: The Welch Foundation; Shell Chemical
Company; ExxonMobil Corporation; Prosortium, Inc.; Slusser, Wilson,
and Partridge LLP; The Seaborg Institute at Los Alamos National
Laboratory; Dr. Stephen G. Baxter; The University of Texas at Austin;
org 001 The University of New Mexico (UNM); and Southern Methodist
acs.7.pr University (SMU). The editors thank their own institutions—SMU,
2, 2009 | http://pubs.0.1021/bk-2005-091 ppUBAuooNCbsoSiMlku ic,sfm o aaD trin aotednhpn de.aS irWratf moncerode vinaaaeltl s rNloaoisg aw getaiir nolaosgtnfoe a tfthlnui miLolsltya eesb dyaof mcorfkarop ntroou osriswiti seult smeoh—d e giplnfpero e CrDpi nhpar ra.ep erSmr tetitepichcpiaipashr ialen btnaigo nn Rogtdhk i iEti.nt sen Ttrbhg hoaeienon sAdkey eCtfmrhoSiern g
October 205 | doi: 1 News (May 10, 2004).
6 on 1, 20 Michael Lattman
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University of New Mexico
Albuquerque, NM 87131
and
Advanced Materials Laboratory
Sandia National Laboratories
1001 University Boulevard, SE
Albuquerque, NM 87106
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In Modern Aspects of Main Group Chemistry; Lattman, M., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
Overview of this Volume
Michael Lattman1 and Richard A. Kemp2,3
1Department of Chemistry, Southern Methodist University, Dallas, TX
75275
2Department of Chemistry, University of New Mexico, MSC03 2060,
Albuquerque, NM 87131
3Sandia National Laboratories, Advanced Materials Laboratory, 1001
University Blvd., SE, Albuquerque, NM 87106
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34.13mber of the future." Main group elements such as magnesium (photosynthesis) and
y 89.163.ate: Dece pmathoeomtsapsl h. cohrueInms oi(rsAgtraTynP i mca napndoy lAy umDsPeer)f sua lrs eul icigmha npadossr pt aconoltyn pitnah iobnsi opmlhoaagizinec nagelr sop,ru ospce emeslsiecemos.ne dnItunsc ttaorasrn gdsroiotniuoopnr
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wnlblic spectrum of main group chemistry, ranging from the fundamental themes of
ou synthesis and bonding to the more applied aspects. Many of these uses for main
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group elements are highlighted below and discussed in more detail in the
individual chapters.
What defines main group chemistry? As with almost all areas currently
in chemistry, the definition seems to be rapidly changing and expanding to areas
previously unforeseen. For the purpose of this symposium, we view main group
chemistry as the study of elements of the s and ρ block, particularly those in
Groups 1, 2, and 13-17. While not strictly in these groups, the elements of
Group 12 are often considered to be main group due to their similarities in
reaction chemistry. All of these elements generally use the outermost s and ρ
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In Modern Aspects of Main Group Chemistry; Lattman, M., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
orbitals in bonding, yet there are no restrictions against expansion of the valence
shell, e.g., in hypervalent compounds.
The book is organized into three broad sections in an effort to categorize the
contributions. This organization is somewhat artificial - there is obvious
overlap, and certain chapters could easily be in other sections. The first section,
Unusual Oxidation States and Bonding, highlights some of the most traditional
aspects of main group chemistry and updates the current state-of-the-art in this
area. The book opens with a chapter by the symposium honoree (Alan H.
Cowley) describing recent developments from his laboratory, particularly with
respect to carbene analogs. This is followed by chapters on aluminum
hydroxides, thiols, selenols, and amides (Herbert W. Roesky) and the
preparation of large gallium sulfide arrays from gallium hydride chlorides
(Hubert Schmidbaur). The next chapter describes electron-deficient
intermediates focusing on four-electron species but also includes six-electron
structures (Peter P. Gaspar). Two chapters on stable phosphorus radicals follow:
the first describes a variety of neutral radical species (Tristram Chivers), while
org 001 the second depicts diradical species containing one bond less than usual valence
acs.7.pr rules predict (Guy Bertrand). The next chapter describes a striking example of
2, 2009 | http://pubs.0.1021/bk-2005-091 uRsssstttonrraeluudeticcedestt r,-uu olsJryrtfreeai .snt )+e a gf1s no h vdrl(oels Coraw.ew shiagoan.ca nrgtslTsi e vi wnspfi ctohoyLrrae .obsa tBhefos e rep.o sd hMtnd ord-uisarfipcesfcehttldoaurooetrrretannuidlocas eln ccdsashh) n a aw(adpnDni tgtaedaherrv s sstMei h ddn4Nea ei4 ncWshd c(ecMr .aa iabHvt i =eio.ed nrtReGh stcae aeoin in,hnl ke Pgyaidedbn fnr))oaoe .r ncrlmysuaC slbay(ihaslWsa nriopeseixtl a-eliloicrdiasktfami evtoti ihoSnteyn.
October 205 | doi: 1 orPifan idgniseb )oa.r naTdn hec(e4a g)la es[stB 2Rtww4] iotch oc mphoapptoetuennrtdsia sol f(a Ntphipicshl iocselaactsito iConn.s Natrooe r mbdoearvnoo)n tae ndpdh t oobs oparhrogindu-eapb hl(oyRs opthbheoe rrmtu soT s.t
136 on er 1, 20 msigunltiifpiclea nbto fnudnsd atom eelnetmale nadtsv abnecleosw i tnh me faiirns tg rroouwp o cfh tehme ipsterryio idni cth tea blales.t 2A5 ycheaaprste r-
34.mb on the history of multiple bonding to silicon (Robert West) is followed by one
y 89.163.ate: Dece osinli creoTcnhe (neP t hsaiedlicvpoa Pnn.cd Pe sos wteoce rtpi)or. enp,a rCe iosoomrdeirnica atilkoenn e Canhaelomgsi sotfr eyl,e mreepnrtse sheenatsv iethr et habnro ad
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wnlblic as well as low molecular aggregation (Michael F. Lappert). This is followed by
DoPu chapters on bidentate Lewis acids with specific fluoride ion binding capabilities
(François P. Gabbaï), new "salen"-type main group ligands for lanthanide metal
ion binding (Richard A. Jones), and die use of calixarenes to control geometries
of main group atoms and ligand-metal interactions (Michael Lattman). Two
chapters follow on N-heterocyclic carbenes. The first describes carbene/high-
oxidation state metal interactions where the carbene displays Lewis acidic
behavior (Colin D. Abemethy), and the second illustrates redox chemistry of the
carbenes (Jason A. C. Clyburne). This section is rounded out by chapters on
phosphorus (III) coordination as a Lewis acid (Neil Burford) and the rich and
varied chemistry of metallacarboranes (Narayan S. Hosmane).
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In Modern Aspects of Main Group Chemistry; Lattman, M., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
The third section, Materials, Polymers, and Other Applications, emphasizes
how the fundamental aspects of main group chemistry are being transformed
into applications. The section opens with a chapter on polyhedral boranes with
applications to nanotechnology, including molecular delivery (M. Frederick
Hawthorne). This is followed by chapters on precursors to (Robert H. Neilson)
and properties of cyclic- and polyphosphazenes (Patty Wisian-Neilson).
Chapters on giant dendrimers (Didier Astruc), boron nanowires (William E.
Buhro), and molecular precursors for CVD of Group 13 chalcogenides (Claire J.
Carmalt) follow. The final three chapters describe the ability of certain boron
chelates to cleave phosphate esters with applications to decontamination of
nerve agents and pesticides (David A. Atwood), the reactions of main group
diamides with carbon dioxide to eventually prepare 11C-labelled
radiopharmaceuticals (Richard A. Kemp), and the biological implications of
tin/sulfur interactions (Keith H. Pannell).
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In Modern Aspects of Main Group Chemistry; Lattman, M., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
