Modern Aspects of Main Group Chemistry PDF
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ACS SYMPOSIUM SERIES 917 Modern Aspects of Main Group Chemistry acs.org 7.fw001 Michael Lattman, Editor bs.91 u0 Southern Methodist University p://p005- 22, 2009 | htt10.1021/bk-2 RiSchaUnandriidvae ANrsa.i ttiyKo onefam Nl Lepaw,b MEordeaixttoiocrroi e s October 05 | doi: 6 on 1, 20 4.13ber 3m ed by 89.163.n Date: Dece ACS DivisionS opfo Innsoorrgeda nbiyc tChhee mistry, Inc do oaati wnlblic ou DP 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 3m ded by 89.163.on Date: Dece cAI1Sh0lBla8 pNR toei gfr1 h t0fhtes:ee R 0oUe-f8s. Se$4r.31 v02Ce.-d0o3.0p9 y2Rpr6lei-ugp6hsr o t$ g0Ara.7cp5th i icps eacrl olpopawygienedg i sfbo perya oiidnnt dteor tn htahale t uCpseoerp myoirntitgleyhd,t pbCryole vaSirdeacentdcioe nt hCsa et1n 0tae7 r ,po eIrnr —c., oaati 222 Rosewood Drive, Danvers, MA 01923, USA. Republication or reproduction for sale wnlblic of pages in this book is permitted only under license fromA CS. Direct these and other ou DP permission requests to ACS Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. 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 bs.91 u0 p://p005- 2, 2009 | htt0.1021/bk-2 21 October 05 | doi: 6 on 1, 20 4.13ber 3m ed by 89.163.n Date: Dece do oaati wnlblic Professor Alan H. Cowley, ou DP 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. acs.org 7.fw001 bs.91 u0 p://p005- 2, 2009 | htt0.1021/bk-2 21 October 05 | doi: 6 on 1, 20 4.13ber 3m ed by 89.163.n Date: Dece do oaati wnlblic ou DP 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 u0 22, 2009 | http://p10.1021/bk-2005- ttcianhehpnteapetp rrsbetoe osiprsotrs kitra oae;te vr ot,iehet h woepev eeraeedsurrv d-mfriioeeeavwrnyi cea e wpbo.p ereSrd ooian mpdptrdrrieoaeio dtdpreua tctpaotoneo r dprfsiry n com oacvmhalid aayppec rcbt eeceheropem stena xpnascircrvlueeeehd aeocendordsdv i reveterdoejan e.gb ecDesetsit rot.aea nnWrf,td sfha oofneconfudr s 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. 3m ed by 89.163.n Date: Dece ACS Books Department do oaati wnlblic ou DP 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 October 05 | doi: WBeeclacuhs eP rPorfoefsessosro ro fC oCwhleemy iwstarys aabt otuhte toU cneivleebrrsaittey hoifs T7e0xth abs iratht dAayu,s twine. 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 ou DP and industrial chemists and materials scientists working in areas related 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. xi 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 13er 34.mb Department of Chemistry y 89.163.ate: Dece DSoaulltahse, rTnX M 7e5th27o5d ist University bD oaded ation Richard A. Kemp wnlblic Department of Chemistry ou D P MSC03 2060 University of New Mexico Albuquerque, NM 87131 and Advanced Materials Laboratory Sandia National Laboratories 1001 University Boulevard, SE Albuquerque, NM 87106 xii 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 org 001 acs.7.pr 22, 2009 | http://pubs.10.1021/bk-2005-091 bmussyieblangiitcqtiehonTurenniihsat,iieo nlssp ug l hoas aofs.w ntsn ipdttawhhn In ooentarhn- un tmeasyon ,-tfa efdutaicen vnmhrdedinaea yomslhsoeleo eapangrroevstyra sio.hele u arasb srS erc meilshemeaa,mek ptnetmelhr yniraa aots ilsruns etga tsvhotgueisrra dogt hs,eui onenpmlvc - pogeaerle ilevneilsni m emn gnmgeret on-tamhdutisoanpu dy lgast cri raopo(eppmul eappup rlb stiociecochudanuent dlimdaioinsnrnil sg ysat tr rhiyiiennn,e October 05 | doi: nsiiltircidaetes acnhdem chisetmryi)c,a allsy wmeoldl ifaiesd i nsi tnhgele p-wreaplalerdat nioann ootufb mesa. teCriaelrsa msuiccsh a nads dbeonrosen 6 on 1, 20 mInatetreersiatilnsg layr,e a amlmaions gt roaullp m elaedmee nuts i-n hgy odxroidgeens, -c aisr bviideewse, dn bityr imdeasn,y o ars bthoer i"dfeuse.l 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 bD oaded ation g1r3o-u1p5 aenledm 1e4n-t1s 6a cso kmepyo cuonmdsp,o cnoeanttisn.g sT, ohreg acnhoampteertasl loicf cthaitsa lbyostosk - caolvl ehra vae b mroaaidn 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 DP 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 xiii 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 bD oaded ation wdeiftihn iati ocnh atphtaetr ioncnl uβd-edsik metoimst itnyapteess, olifg daonndosr /wachciecpht ostra bbiolnizdes .l oTwh oisx sidecattiioonn osptaetness 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). xiv 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). org 001 acs.7.pr 2, 2009 | http://pubs.0.1021/bk-2005-091 21 October 05 | doi: 6 on 1, 20 13er 34.mb y 89.163.ate: Dece bD oaded ation wnlblic ou DP xv In Modern Aspects of Main Group Chemistry; Lattman, M., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2005.
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