<!DOCTYPE html PUBLIC "-//W3C//DTD XHTML 1.0 Transitional//EN"
"http://www.w3.org/TR/xhtml1/DTD/xhtml1-transitional.dtd">
<html>
<head>
<title>UTas ePrints - Organoplatinum(II) and -(IV) and Organopalladium(II) and -(IV) Complexes of a Macrocyclic Thioether: X-ray Crystal Structure of Pt(C6H5)2(9S3), an Example of Exodentate 1,4,7-Trithiacyclononane (9S3)</title>
<script type="text/javascript" src="http://eprints.utas.edu.au/javascript/auto.js"><!-- padder --></script>
<style type="text/css" media="screen">@import url(http://eprints.utas.edu.au/style/auto.css);</style>
<style type="text/css" media="print">@import url(http://eprints.utas.edu.au/style/print.css);</style>
<link rel="icon" href="/images/eprints/favicon.ico" type="image/x-icon" />
<link rel="shortcut icon" href="/images/eprints/favicon.ico" type="image/x-icon" />
<link rel="Top" href="http://eprints.utas.edu.au/" />
<link rel="Search" href="http://eprints.utas.edu.au/cgi/search" />
<meta content="Bennett, M.A." name="eprints.creators_name" />
<meta content="Canty, A.J." name="eprints.creators_name" />
<meta content="Felixberger, J.F." name="eprints.creators_name" />
<meta content="Rendina, L.M." name="eprints.creators_name" />
<meta content="Sunderland, C." name="eprints.creators_name" />
<meta content="Willis, A.C." name="eprints.creators_name" />
<meta name="eprints.creators_id" />
<meta content="allan.canty@utas.edu.au" name="eprints.creators_id" />
<meta name="eprints.creators_id" />
<meta name="eprints.creators_id" />
<meta name="eprints.creators_id" />
<meta name="eprints.creators_id" />
<meta content="article" name="eprints.type" />
<meta content="2008-01-14 04:09:33" name="eprints.datestamp" />
<meta content="2008-01-18T02:32:32Z" name="eprints.lastmod" />
<meta content="show" name="eprints.metadata_visibility" />
<meta content="Organoplatinum(II) and -(IV) and Organopalladium(II) and -(IV) Complexes of a Macrocyclic Thioether: X-ray Crystal Structure of Pt(C6H5)2(9S3), an Example of Exodentate
1,4,7-Trithiacyclononane (9S3)" name="eprints.title" />
<meta content="pub" name="eprints.ispublished" />
<meta content="259901" name="eprints.subjects" />
<meta content="restricted" name="eprints.full_text_status" />
<meta content="Displacement of coordinated 1,5-cyclooctadiene or norbornadiene from suitable precursors has given a series of hapto1-C-bonded organoplatinum(II) complexes containing 1,4,7-trithiacyclononane (9S3), i.e. PtRR’(9S3) [R = R’
= Me(l), Et(2), CH2CMe3(3), CH2SiMe3(4), Ph(5); R = Me, R’ = CH2SiMe3(6); R = C1, R’ = CH2SiMe3(7)]. The dimethylpalladium(II) complex PdMe2(9S3)(8) has been obtained similarly from PdMe2(tetramethylethylenediamine),
but Pd(CH2SiMe3)2(9S3)(9) could not be isolated in a pure state. Crystals of 5 are orthorhombic, space group Pbca, with a = 12.047(1) A, b = 17.660(2) A, c = 16.854(2) A, and Z = 8. The structure was solved by heavy-atom methods and refined by least squares analysis to R = 0.031 and R, = 0.046 for 2498 unique observed reflections. The platinum atom is bound to two sulfur atoms of bidentate 9S3 and to two cis-phenyl groups in an almost planar array. The macrocyclic thioether adopts an exodentate conformation such that the uncoordinated sulfur atom points away from the metal atom, in contrast to the more usual endodentate conformation found in PdX2(9S3) (X = C1, Br). At room temperature, the 9S3 CH2 resonances in the 1H and 13C{H} NMR spectra of 1-7 are broad; variable-temperature NMR studies of 2 and 4 suggest that this is caused by exchange of free and coordinated sulfur atoms. Complexes 3 and 4 react with halogens to give diorganoplatinum(IV) salts [PtXR2(9S3)]X [R = CH2SiMe3, X = I(l0), Br(11); R = CH2CMe3, X = I(13)], and 1 and 2 oxidatively add methyl or ethyl iodide to give triorganoplatinum(IV) salts [PtR2R’(9S3)]1 [R = R’ = Me(14); R = Et, R’ = Me(15); R = R’ = Et(16)]; in these products 9S3 is probably tridentate. The palladium(II) complex 8 likewise adds methyl iodide to give [PdMe3(9S3)]I(17), which can be converted into a nitrate salt [PdMe3(9S3)]N03(18). These compounds show no tendency to reductively eliminate ethane, and they are the first isolable organopalladium(IV) complexes that do not contain a nitrogen donor, thus demonstrating the ability of endodentate 9S3 to stabilize octahedral or pseudooctahedral geometries." name="eprints.abstract" />
<meta content="1993" name="eprints.date" />
<meta content="published" name="eprints.date_type" />
<meta content="Inorganic Chemistry" name="eprints.publication" />
<meta content="32" name="eprints.volume" />
<meta content="10" name="eprints.number" />
<meta content="1951-1958" name="eprints.pagerange" />
<meta content="10.1021/ic00062a013" name="eprints.id_number" />
<meta content="TRUE" name="eprints.refereed" />
<meta content="0020-1669" name="eprints.issn" />
<meta content="http://dx.doi.org/10.1021/ic00062a013" name="eprints.official_url" />
<meta content="(1) Permanent address: Department of Chemistry, The University of
Tasmania, Hobart, Tasmania 7001, Australia.
(2) Other abbreviations: cod = 1,5-cyclooctadiene; nbd = norbornadiene;
tmeda = N,N,N’,N’-tetramethylethylenediami(npez;) ,CH = tris(1-
pyrazoly1)methane.
(3)Cooper, S. R.; Rawle, S. C. Struct. Bonding 1990, 72, 1.
(4)Blake, A. J.; Schriider, M. Adv. Inorg. Chem. 1990, 35, 1.
(5)Blake, A. J.; Holder, A. J.; Roberts, Y. V.;Schrader, M. Acta Crystallogr.,
Sect. C 1988, 44, 360.
(6)Wieghardt, K.; Kiippers, H.-J.; Raabe, E.; Kriiger, C. Angew. Chem.,
h i . Ed. Engl. 1986, 25, 1101.
(7) Blake, A. J.; Holder, A. J.; Hyde, T. I.; Roberts, Y. V.; Lavery, A. J.;
Schrbder, M. J. Organomet. Chem. 1987, 323, 261.
(8) Blake, A. J.; Gould, R. 0.; Holder, A. J.; Hyde, T. I.; Odulate, M. 0.;
Lavery, A. J.; Schrsder, M. J. Chem. SOC.C, hem. Commun. 1987,118.
(9) Blake, A. J.; Holder A. J.; Hyde, T. I.; Schriider, M. J. Chem. SOC.,
Chem. Commun. 1987, 987.
(10) Schriider, M. Pure Appl. Chem. 1988, 60, 517.
(11) Abel, E. W.; Beer, P. D.; Moss, I.; Orrell, K. G.; Sik, V.; Bates, P. A,;
Hursthouse, M. B. J. Chem. SOC., Chem. Commun. 1987, 978; J.
Organomet. Chem. 1988, 341, 559.
(12) Hartley, F. R. In ComprehensiveOrganometallicChemistryW; ilkinson,
G., Stone, F. G. A., Abel, E. W., Ed.; Pergamon Press: Oxford, England,
1982; Vol. 6, p 471.
(13)Canty, A. J. Acc. Chem. Res. 1992,25,83, and references cited therein.
(14)(a) Byers, P. K.; Canty, A. J.; Skelton, B. W.; White, A. H. J. Chem.
Soc., Chem. Commun. 1987,1093. (b) Byers, P. K.; Canty, A. J. Ibid.
1988,639; (c) Byers, P. K.; Canty, A. J.; Skelton, B. W.; White, A. H.
Oraanomerallics 1990, 9, 826. (d) Brown. D. G.; Byers, P. K.; Canty,
A.-J. Ibid. 1990, 9, 1231.
(15) Blower, P. J.; Cooper, S. R. Inorg. Chem. 1987, 26, 2009.
(16) Clark, H. C.; Manzer, L. E. J. Organomet. Chem. 1973, 59, 411.
(17) Bassan, R.; Bryars, K. H.; Judd, L.; Platt, A. W. G.; Pringle, P. G. Inorg.
(18) Brainard, R. L.; Miller, T. M.; Whitesides, G. M. Organometallics 1986,
(19) de Graaf, W.; Boersma, J.; Smeets, W. J. J.; Spek, A. L.; van Koten,
Chim. Acta 1986, 121, L41.
5, 1481.
G. Organometallics 1989, 8, 2907.
(20) Churchill, M. R.; Kalra, K. L. Inorg. Chem. 1974, 13, 1427.
(21) Sheldrick, G. M. In Crystallographic Computing3; Sheldrick, G. M.,
Kriiger, C., Goddard, R., Ed.; Oxford University Press: London, 1985;
p 175.
(22) International Tables forX-ray Crystallography; Ibers, J. A., Hamilton,
W. C., Ed.; Kynoch Press: Birmingham, England, 1974; Vol. 4;
distributed by Kluwer Academic Publishers, Dordrecht, Holland.
(23) XTAL 3.0 Reference Manual; Hall, S. R., Stewart, J. M., Eds.;
Universities of Western Australia and Maryland: Nedlands, Australia,
and College Park, MD,
(24) Kuyper, J.; van der Laan, R.; Jeanneaus, F.; Vrieze, K. Transition Met.
(25) Wozniak, B.; Ruddick, J. D.; Wilkinson,G.J . Chem. SOCA. 1971,3116.
(26) (a) Appleton, T. G.; Clark, H. C.; Manzer, L. E. Coord. Chem. Rev.
1973, IO, 335. (b) Chisholm, M. H.; Clark, H. C.; Manzer, L. E.;
Stothers, J. B.; Ward, J. E. H. J. Am. Chem. SOC. 1975, 97, 721.
27) Hanan,G. S.; Kickham, J. E.; Loeb, S. J. J. Chem.Soc., Chem. Commun.
(28) Braterman,P. S.; Cross, R. J.; ManojloviC-Muir. L.; Muir, K. W.; Young,
(29) Bresciani-Pahor, N.; Plazzotta, M.; Randaccio, L.; Bruno, G.; Ricevuto,
(30) Gee, R. J. D.; Powell, H. M. J. Chem. SOC. A 1971, 1956.
1991, 893.
G. B. J. Organomet. Chem. 1975, 84, C40.
V.; Romeo, R.; Belluco, U. Inorg. Chim. Acta 1978, 31, 171.
(31) The basis of this assignment is an assumed analogy with the observed
Karplus-type angular dependence of the magnitudes of the coupling
constants )Jp,.N.~a.nHd 4Jp,-h c H in amino acid and chelating diamine
complexes of platin~m(II).~~.~’
(32) Erikson, L. E.; McDonald, J. W.; Howie, J. K.; Clow, R. P. J. Am.
Chem. SOC. 1968, 90,6371.
(33) Appleton, T. G.; Hall, J. R. Inorg. Chem. 1971, 10. 1717.
(34) Abel, E. W.; Booth, M.; King, G.; Orrell, K. G.; Pring, G. M.; Sik, V.
J. Chem. Soc.. Dalton Trans. 1981, 1846. Abel, E. W.; King, G. D.;
Orrell, K. G.; Sik, V.; Cameron, T. S.; Jochem, K. Ibid. 1984, 2047.
35) Calvin, G.; Coates, G. E. J. Chem. SOC. 1960, 2008.
(36) Adams,D. M.;Chatt, J.;Shaw,B. L. J. Chem.Soc. 1960,2047. Adams,
D.M. Zbid. 1962, 1220.
(37) Pregosin, P. S. Coord. Chem. Rev. 1982, 44, 247.
(38) Canty, A. J.; Honeyman, R. T.; Skelton, B. W.; White, A. H. J.
Organomet. Chem. 1990, 396, 105.
(39) Chatt, J.: Shaw, B. L. J. Chem. SOC. 1959, 705.
(40) Gulliver, D. J.; Levason, W. J. Chem. SOC.D, alton Trans. 1982, 1895." name="eprints.referencetext" />
<meta content="Bennett, M.A. and Canty, A.J. and Felixberger, J.F. and Rendina, L.M. and Sunderland, C. and Willis, A.C. (1993) Organoplatinum(II) and -(IV) and Organopalladium(II) and -(IV) Complexes of a Macrocyclic Thioether: X-ray Crystal Structure of Pt(C6H5)2(9S3), an Example of Exodentate 1,4,7-Trithiacyclononane (9S3). Inorganic Chemistry, 32 (10). pp. 1951-1958. ISSN 0020-1669" name="eprints.citation" />
<meta content="http://eprints.utas.edu.au/2863/1/IC1993_2C_1951.pdf" name="eprints.document_url" />
<link rel="schema.DC" href="http://purl.org/DC/elements/1.0/" />
<meta content="Organoplatinum(II) and -(IV) and Organopalladium(II) and -(IV) Complexes of a Macrocyclic Thioether: X-ray Crystal Structure of Pt(C6H5)2(9S3), an Example of Exodentate
1,4,7-Trithiacyclononane (9S3)" name="DC.title" />
<meta content="Bennett, M.A." name="DC.creator" />
<meta content="Canty, A.J." name="DC.creator" />
<meta content="Felixberger, J.F." name="DC.creator" />
<meta content="Rendina, L.M." name="DC.creator" />
<meta content="Sunderland, C." name="DC.creator" />
<meta content="Willis, A.C." name="DC.creator" />
<meta content="259901 Organometallic Chemistry" name="DC.subject" />
<meta content="Displacement of coordinated 1,5-cyclooctadiene or norbornadiene from suitable precursors has given a series of hapto1-C-bonded organoplatinum(II) complexes containing 1,4,7-trithiacyclononane (9S3), i.e. PtRR’(9S3) [R = R’
= Me(l), Et(2), CH2CMe3(3), CH2SiMe3(4), Ph(5); R = Me, R’ = CH2SiMe3(6); R = C1, R’ = CH2SiMe3(7)]. The dimethylpalladium(II) complex PdMe2(9S3)(8) has been obtained similarly from PdMe2(tetramethylethylenediamine),
but Pd(CH2SiMe3)2(9S3)(9) could not be isolated in a pure state. Crystals of 5 are orthorhombic, space group Pbca, with a = 12.047(1) A, b = 17.660(2) A, c = 16.854(2) A, and Z = 8. The structure was solved by heavy-atom methods and refined by least squares analysis to R = 0.031 and R, = 0.046 for 2498 unique observed reflections. The platinum atom is bound to two sulfur atoms of bidentate 9S3 and to two cis-phenyl groups in an almost planar array. The macrocyclic thioether adopts an exodentate conformation such that the uncoordinated sulfur atom points away from the metal atom, in contrast to the more usual endodentate conformation found in PdX2(9S3) (X = C1, Br). At room temperature, the 9S3 CH2 resonances in the 1H and 13C{H} NMR spectra of 1-7 are broad; variable-temperature NMR studies of 2 and 4 suggest that this is caused by exchange of free and coordinated sulfur atoms. Complexes 3 and 4 react with halogens to give diorganoplatinum(IV) salts [PtXR2(9S3)]X [R = CH2SiMe3, X = I(l0), Br(11); R = CH2CMe3, X = I(13)], and 1 and 2 oxidatively add methyl or ethyl iodide to give triorganoplatinum(IV) salts [PtR2R’(9S3)]1 [R = R’ = Me(14); R = Et, R’ = Me(15); R = R’ = Et(16)]; in these products 9S3 is probably tridentate. The palladium(II) complex 8 likewise adds methyl iodide to give [PdMe3(9S3)]I(17), which can be converted into a nitrate salt [PdMe3(9S3)]N03(18). These compounds show no tendency to reductively eliminate ethane, and they are the first isolable organopalladium(IV) complexes that do not contain a nitrogen donor, thus demonstrating the ability of endodentate 9S3 to stabilize octahedral or pseudooctahedral geometries." name="DC.description" />
<meta content="1993" name="DC.date" />
<meta content="Article" name="DC.type" />
<meta content="PeerReviewed" name="DC.type" />
<meta content="application/pdf" name="DC.format" />
<meta content="http://eprints.utas.edu.au/2863/1/IC1993_2C_1951.pdf" name="DC.identifier" />
<meta content="http://dx.doi.org/10.1021/ic00062a013" name="DC.relation" />
<meta content="Bennett, M.A. and Canty, A.J. and Felixberger, J.F. and Rendina, L.M. and Sunderland, C. and Willis, A.C. (1993) Organoplatinum(II) and -(IV) and Organopalladium(II) and -(IV) Complexes of a Macrocyclic Thioether: X-ray Crystal Structure of Pt(C6H5)2(9S3), an Example of Exodentate 1,4,7-Trithiacyclononane (9S3). Inorganic Chemistry, 32 (10). pp. 1951-1958. ISSN 0020-1669" name="DC.identifier" />
<meta content="http://eprints.utas.edu.au/2863/" name="DC.relation" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/BibTeX/epprod-eprint-2863.bib" title="BibTeX" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/ContextObject/epprod-eprint-2863.xml" title="OpenURL ContextObject" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/ContextObject::Dissertation/epprod-eprint-2863.xml" title="OpenURL Dissertation" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/ContextObject::Journal/epprod-eprint-2863.xml" title="OpenURL Journal" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/DC/epprod-eprint-2863.txt" title="Dublin Core" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/DIDL/epprod-eprint-2863.xml" title="DIDL" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/EndNote/epprod-eprint-2863.enw" title="EndNote" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/HTML/epprod-eprint-2863.html" title="HTML Citation" type="text/html; charset=utf-8" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/METS/epprod-eprint-2863.xml" title="METS" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/MODS/epprod-eprint-2863.xml" title="MODS" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/RIS/epprod-eprint-2863.ris" title="Reference Manager" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/Refer/epprod-eprint-2863.refer" title="Refer" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/Simple/epprod-eprint-2863text" title="Simple Metadata" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/Text/epprod-eprint-2863.txt" title="ASCII Citation" type="text/plain; charset=utf-8" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2863/XML/epprod-eprint-2863.xml" title="EP3 XML" type="text/xml" />
</head>
<body bgcolor="#ffffff" text="#000000" onLoad="loadRoutine(); MM_preloadImages('images/eprints/ePrints_banner_r5_c5_f2.gif','images/eprints/ePrints_banner_r5_c7_f2.gif','images/eprints/ePrints_banner_r5_c8_f2.gif','images/eprints/ePrints_banner_r5_c9_f2.gif','images/eprints/ePrints_banner_r5_c10_f2.gif','images/eprints/ePrints_banner_r5_c11_f2.gif','images/eprints/ePrints_banner_r6_c4_f2.gif')">
<div class="ep_noprint"><noscript><style type="text/css">@import url(http://eprints.utas.edu.au/style/nojs.css);</style></noscript></div>
<table width="795" border="0" cellspacing="0" cellpadding="0">
<tr>
<td><script language="JavaScript1.2">mmLoadMenus();</script>
<table border="0" cellpadding="0" cellspacing="0" width="795">
<!-- fwtable fwsrc="eprints_banner_final2.png" fwbase="ePrints_banner.gif" fwstyle="Dreamweaver" fwdocid = "1249563342" fwnested="0" -->
<tr>
<td><img src="/images/eprints/spacer.gif" width="32" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="104" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="44" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="105" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="41" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="16" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="68" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="68" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="68" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="82" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="69" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="98" height="1" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="1" height="1" border="0" alt="" /></td>
</tr>
<tr>
<td colspan="12"><img name="ePrints_banner_r1_c1" src="/images/eprints/ePrints_banner_r1_c1.gif" width="795" height="10" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="1" height="10" border="0" alt="" /></td>
</tr>
<tr>
<td rowspan="6"><img name="ePrints_banner_r2_c1" src="/images/eprints/ePrints_banner_r2_c1.gif" width="32" height="118" border="0" alt="" /></td>
<td rowspan="5"><a href="http://www.utas.edu.au/"><img name="ePrints_banner_r2_c2" src="/images/eprints/ePrints_banner_r2_c2.gif" width="104" height="103" border="0" alt="" /></a></td>
<td colspan="10"><img name="ePrints_banner_r2_c3" src="/images/eprints/ePrints_banner_r2_c3.gif" width="659" height="41" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="1" height="41" border="0" alt="" /></td>
</tr>
<tr>
<td colspan="3"><a href="http://eprints.utas.edu.au/"><img name="ePrints_banner_r3_c3" src="/images/eprints/ePrints_banner_r3_c3.gif" width="190" height="31" border="0" alt="" /></a></td>
<td rowspan="2" colspan="7"><img name="ePrints_banner_r3_c6" src="/images/eprints/ePrints_banner_r3_c6.gif" width="469" height="37" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="1" height="31" border="0" alt="" /></td>
</tr>
<tr>
<td colspan="3"><img name="ePrints_banner_r4_c3" src="/images/eprints/ePrints_banner_r4_c3.gif" width="190" height="6" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="1" height="6" border="0" alt="" /></td>
</tr>
<tr>
<td colspan="2"><img name="ePrints_banner_r5_c3" src="/images/eprints/ePrints_banner_r5_c3.gif" width="149" height="1" border="0" alt="" /></td>
<td rowspan="2" colspan="2"><a href="/information.html" onMouseOut="MM_swapImgRestore();MM_startTimeout()" onMouseOver="MM_showMenu(window.mm_menu_0821132634_0,0,25,null,'ePrints_banner_r5_c5');MM_swapImage('ePrints_banner_r5_c5','','/images/eprints/ePrints_banner_r5_c5_f2.gif',1);"><img name="ePrints_banner_r5_c5" src="/images/eprints/ePrints_banner_r5_c5.gif" width="57" height="25" border="0" alt="About" /></a></td>
<td rowspan="2"><a href="/view/" onMouseOut="MM_swapImgRestore();MM_startTimeout()" onMouseOver="MM_showMenu(window.mm_menu_0821133021_1,0,25,null,'ePrints_banner_r5_c7');MM_swapImage('ePrints_banner_r5_c7','','/images/eprints/ePrints_banner_r5_c7_f2.gif',1);"><img name="ePrints_banner_r5_c7" src="/images/eprints/ePrints_banner_r5_c7.gif" width="68" height="25" border="0" alt="Browse" /></a></td>
<td rowspan="2"><a href="/perl/search/simple" onMouseOut="MM_swapImgRestore();MM_startTimeout()" onMouseOver="MM_showMenu(window.mm_menu_0821133201_2,0,25,null,'ePrints_banner_r5_c8');MM_swapImage('ePrints_banner_r5_c8','','/images/eprints/ePrints_banner_r5_c8_f2.gif',1);"><img name="ePrints_banner_r5_c8" src="/images/eprints/ePrints_banner_r5_c8.gif" width="68" height="25" border="0" alt="Search" /></a></td>
<td rowspan="2"><a href="/perl/register" onMouseOut="MM_swapImgRestore();MM_startTimeout();" onMouseOver="MM_showMenu(window.mm_menu_1018171924_3,0,25,null,'ePrints_banner_r5_c9');MM_swapImage('ePrints_banner_r5_c9','','/images/eprints/ePrints_banner_r5_c9_f2.gif',1);"><img name="ePrints_banner_r5_c9" src="/images/eprints/ePrints_banner_r5_c9.gif" width="68" height="25" border="0" alt="register" /></a></td>
<td rowspan="2"><a href="/perl/users/home" onMouseOut="MM_swapImgRestore();MM_startTimeout()" onMouseOver="MM_showMenu(window.mm_menu_0821133422_4,0,25,null,'ePrints_banner_r5_c10');MM_swapImage('ePrints_banner_r5_c10','','/images/eprints/ePrints_banner_r5_c10_f2.gif',1);"><img name="ePrints_banner_r5_c10" src="/images/eprints/ePrints_banner_r5_c10.gif" width="82" height="25" border="0" alt="user area" /></a></td>
<td rowspan="2"><a href="/help/" onMouseOut="MM_swapImgRestore();MM_startTimeout()" onMouseOver="MM_showMenu(window.mm_menu_0821133514_5,0,25,null,'ePrints_banner_r5_c11');MM_swapImage('ePrints_banner_r5_c11','','/images/eprints/ePrints_banner_r5_c11_f2.gif',1);"><img name="ePrints_banner_r5_c11" src="/images/eprints/ePrints_banner_r5_c11.gif" width="69" height="25" border="0" alt="Help" /></a></td>
<td rowspan="3" colspan="4"><img name="ePrints_banner_r5_c12" src="/images/eprints/ePrints_banner_r5_c12.gif" width="98" height="40" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="1" height="1" border="0" alt="" /></td>
</tr>
<tr>
<td rowspan="2"><img name="ePrints_banner_r6_c3" src="/images/eprints/ePrints_banner_r6_c3.gif" width="44" height="39" border="0" alt="ePrints home" /></td>
<td><a href="/" onMouseOut="MM_swapImgRestore()" onMouseOver="MM_swapImage('ePrints_banner_r6_c4','','/images/eprints/ePrints_banner_r6_c4_f2.gif',1);"><img name="ePrints_banner_r6_c4" src="/images/eprints/ePrints_banner_r6_c4.gif" width="105" height="24" border="0" alt="ePrints home" /></a></td>
<td><img src="/images/eprints/spacer.gif" width="1" height="24" border="0" alt="" /></td>
</tr>
<tr>
<td><img name="ePrints_banner_r7_c2" src="/images/eprints/ePrints_banner_r7_c2.gif" width="104" height="15" border="0" alt="" /></td>
<td colspan="8"><img name="ePrints_banner_r7_c4" src="/images/eprints/ePrints_banner_r7_c4.gif" width="517" height="15" border="0" alt="" /></td>
<td><img src="/images/eprints/spacer.gif" width="1" height="15" border="0" alt="" /></td>
</tr>
</table></td>
</tr>
<tr><td><table width="100%" style="font-size: 90%; border: solid 1px #ccc; padding: 3px"><tr>
<td align="left"><a href="http://eprints.utas.edu.au/cgi/users/home">Login</a> | <a href="http://eprints.utas.edu.au/cgi/register">Create Account</a></td>
<td align="right" style="white-space: nowrap">
<form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/search" style="display:inline">
<input class="ep_tm_searchbarbox" size="20" type="text" name="q" />
<input class="ep_tm_searchbarbutton" value="Search" type="submit" name="_action_search" />
<input type="hidden" name="_order" value="bytitle" />
<input type="hidden" name="basic_srchtype" value="ALL" />
<input type="hidden" name="_satisfyall" value="ALL" />
</form>
</td>
</tr></table></td></tr>
<tr>
<td class="toplinks"><!-- InstanceBeginEditable name="content" -->
<div align="center">
<table width="720" class="ep_tm_main"><tr><td align="left">
<h1 class="ep_tm_pagetitle">Organoplatinum(II) and -(IV) and Organopalladium(II) and -(IV) Complexes of a Macrocyclic Thioether: X-ray Crystal Structure of Pt(C6H5)2(9S3), an Example of Exodentate 1,4,7-Trithiacyclononane (9S3)</h1>
<p style="margin-bottom: 1em" class="not_ep_block"><span class="person_name">Bennett, M.A.</span> and <span class="person_name">Canty, A.J.</span> and <span class="person_name">Felixberger, J.F.</span> and <span class="person_name">Rendina, L.M.</span> and <span class="person_name">Sunderland, C.</span> and <span class="person_name">Willis, A.C.</span> (1993) <xhtml:em>Organoplatinum(II) and -(IV) and Organopalladium(II) and -(IV) Complexes of a Macrocyclic Thioether: X-ray Crystal Structure of Pt(C6H5)2(9S3), an Example of Exodentate 1,4,7-Trithiacyclononane (9S3).</xhtml:em> Inorganic Chemistry, 32 (10). pp. 1951-1958. ISSN 0020-1669</p><p style="margin-bottom: 1em" class="not_ep_block"></p><table style="margin-bottom: 1em" class="not_ep_block"><tr><td valign="top" style="text-align:center"><a href="http://eprints.utas.edu.au/2863/1/IC1993_2C_1951.pdf"><img alt="[img]" src="http://eprints.utas.edu.au/style/images/fileicons/application_pdf.png" border="0" class="ep_doc_icon" /></a></td><td valign="top"><a href="http://eprints.utas.edu.au/2863/1/IC1993_2C_1951.pdf"><span class="ep_document_citation">PDF</span></a> - Full text restricted - Requires a PDF viewer<br />934Kb</td><td><form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/request_doc"><input value="4083" name="docid" accept-charset="utf-8" type="hidden" /><div class=""><input value="Request a copy" name="_action_null" class="ep_form_action_button" onclick="return EPJS_button_pushed( '_action_null' )" type="submit" /> </div></form></td></tr></table><p style="margin-bottom: 1em" class="not_ep_block">Official URL: <a href="http://dx.doi.org/10.1021/ic00062a013">http://dx.doi.org/10.1021/ic00062a013</a></p><div class="not_ep_block"><h2>Abstract</h2><p style="padding-bottom: 16px; text-align: left; margin: 1em auto 0em auto">Displacement of coordinated 1,5-cyclooctadiene or norbornadiene from suitable precursors has given a series of hapto1-C-bonded organoplatinum(II) complexes containing 1,4,7-trithiacyclononane (9S3), i.e. PtRR’(9S3) [R = R’
= Me(l), Et(2), CH2CMe3(3), CH2SiMe3(4), Ph(5); R = Me, R’ = CH2SiMe3(6); R = C1, R’ = CH2SiMe3(7)]. The dimethylpalladium(II) complex PdMe2(9S3)(8) has been obtained similarly from PdMe2(tetramethylethylenediamine),
but Pd(CH2SiMe3)2(9S3)(9) could not be isolated in a pure state. Crystals of 5 are orthorhombic, space group Pbca, with a = 12.047(1) A, b = 17.660(2) A, c = 16.854(2) A, and Z = 8. The structure was solved by heavy-atom methods and refined by least squares analysis to R = 0.031 and R, = 0.046 for 2498 unique observed reflections. The platinum atom is bound to two sulfur atoms of bidentate 9S3 and to two cis-phenyl groups in an almost planar array. The macrocyclic thioether adopts an exodentate conformation such that the uncoordinated sulfur atom points away from the metal atom, in contrast to the more usual endodentate conformation found in PdX2(9S3) (X = C1, Br). At room temperature, the 9S3 CH2 resonances in the 1H and 13C{H} NMR spectra of 1-7 are broad; variable-temperature NMR studies of 2 and 4 suggest that this is caused by exchange of free and coordinated sulfur atoms. Complexes 3 and 4 react with halogens to give diorganoplatinum(IV) salts [PtXR2(9S3)]X [R = CH2SiMe3, X = I(l0), Br(11); R = CH2CMe3, X = I(13)], and 1 and 2 oxidatively add methyl or ethyl iodide to give triorganoplatinum(IV) salts [PtR2R’(9S3)]1 [R = R’ = Me(14); R = Et, R’ = Me(15); R = R’ = Et(16)]; in these products 9S3 is probably tridentate. The palladium(II) complex 8 likewise adds methyl iodide to give [PdMe3(9S3)]I(17), which can be converted into a nitrate salt [PdMe3(9S3)]N03(18). These compounds show no tendency to reductively eliminate ethane, and they are the first isolable organopalladium(IV) complexes that do not contain a nitrogen donor, thus demonstrating the ability of endodentate 9S3 to stabilize octahedral or pseudooctahedral geometries.</p></div><table style="margin-bottom: 1em" border="0" cellpadding="3" class="not_ep_block"><tr><th valign="top" class="ep_row">Item Type:</th><td valign="top" class="ep_row">Article</td></tr><tr><th valign="top" class="ep_row">Subjects:</th><td valign="top" class="ep_row"><a href="http://eprints.utas.edu.au/view/subjects/259901.html">250000 Chemical Sciences > 259900 Other Chemical Sciences > 259901 Organometallic Chemistry</a></td></tr><tr><th valign="top" class="ep_row">Collections:</th><td valign="top" class="ep_row">UNSPECIFIED</td></tr><tr><th valign="top" class="ep_row">ID Code:</th><td valign="top" class="ep_row">2863</td></tr><tr><th valign="top" class="ep_row">Deposited By:</th><td valign="top" class="ep_row"><span class="ep_name_citation"><span class="person_name">Prof Allan J Canty</span></span></td></tr><tr><th valign="top" class="ep_row">Deposited On:</th><td valign="top" class="ep_row">14 Jan 2008 15:09</td></tr><tr><th valign="top" class="ep_row">Last Modified:</th><td valign="top" class="ep_row">18 Jan 2008 13:32</td></tr><tr><th valign="top" class="ep_row">ePrint Statistics:</th><td valign="top" class="ep_row"><a target="ePrintStats" href="/es/index.php?action=show_detail_eprint;id=2863;">View statistics for this ePrint</a></td></tr></table><p align="right">Repository Staff Only: <a href="http://eprints.utas.edu.au/cgi/users/home?screen=EPrint::View&eprintid=2863">item control page</a></p>
</td></tr></table>
</div>
<!-- InstanceEndEditable --></td>
</tr>
<tr>
<td><!-- #BeginLibraryItem "/Library/footer_eprints.lbi" -->
<table width="795" border="0" align="left" cellpadding="0" class="footer">
<tr valign="top">
<td colspan="2"><div align="center"><a href="http://www.utas.edu.au">UTAS home</a> | <a href="http://www.utas.edu.au/library/">Library home</a> | <a href="/">ePrints home</a> | <a href="/contact.html">contact</a> | <a href="/information.html">about</a> | <a href="/view/">browse</a> | <a href="/perl/search/simple">search</a> | <a href="/perl/register">register</a> | <a href="/perl/users/home">user area</a> | <a href="/help/">help</a></div><br /></td>
</tr>
<tr><td colspan="2"><p><img src="/images/eprints/footerline.gif" width="100%" height="4" /></p></td></tr>
<tr valign="top">
<td width="68%" class="footer">Authorised by the University Librarian<br />
© University of Tasmania ABN 30 764 374 782<br />
<a href="http://www.utas.edu.au/cricos/">CRICOS Provider Code 00586B</a> | <a href="http://www.utas.edu.au/copyright/copyright_disclaimers.html">Copyright & Disclaimers</a> | <a href="http://www.utas.edu.au/accessibility/index.html">Accessibility</a> | <a href="http://eprints.utas.edu.au/feedback/">Site Feedback</a> </td>
<td width="32%"><div align="right">
<p align="right" class="NoPrint"><a href="http://www.utas.edu.au/"><img src="http://www.utas.edu.au/shared/logos/unioftasstrip.gif" alt="University of Tasmania Home Page" width="260" height="16" border="0" align="right" /></a></p>
<p align="right" class="NoPrint"><a href="http://www.utas.edu.au/"><br />
</a></p>
</div></td>
</tr>
<tr valign="top">
<td><p> </p></td>
<td><div align="right"><span class="NoPrint"><a href="http://www.eprints.org/software/"><img src="/images/eprintslogo.gif" alt="ePrints logo" width="77" height="29" border="0" align="bottom" /></a></span></div></td>
</tr>
</table>
<!-- #EndLibraryItem -->
<div align="center"></div></td>
</tr>
</table>
</body>
</html>
