<!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 - Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II)</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="Markies, B.A." name="eprints.creators_name" />
<meta content="Canty, A.J." name="eprints.creators_name" />
<meta content="Boersma, J." name="eprints.creators_name" />
<meta content="van Koten, G." name="eprints.creators_name" />
<meta content="" name="eprints.creators_id" />
<meta content="allan.canty@utas.edu.au" name="eprints.creators_id" />
<meta content="" name="eprints.creators_id" />
<meta content="" name="eprints.creators_id" />
<meta content="article" name="eprints.type" />
<meta content="2008-01-15T01:08:16Z" name="eprints.datestamp" />
<meta content="2008-01-15T01:08:16Z" name="eprints.lastmod" />
<meta content="show" name="eprints.metadata_visibility" />
<meta content="Phenylpalladium(IV) Chemistry: Selectivity in Reductive
Elimination from Palladium(IV) Complexes and Alkyl
Halide Transfer from Palladium(IV) to Palladium(II)" 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="Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-bipyridyl) in acetone at 0 C to form the isolable fac-triorganopalladium(IV) complexes PdIMe2Ph(bpy) (3) and PdXMePh(CH2Ph)(bpy) [X = Br (4), I (5)]. Complex 3 occurs as a mixture of isomers in a ca. 1:l ratio, involving the phenyl group in a position trans either to bpy (3a) or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has
the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal bonded to three different groups could be studied for the first time. The complexes undergo facile reductive elimination in (CD3)2CO at 0 C, in which PdIMe2Ph(bpy) gives a mixture of ethane and toluene in a 4:l molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh(CH2Ph)(bpy) (X = Br, I) gives exclusively toluene and PdX(CH2Ph)(bpy). The analogous tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts more slowly than PdMePh(bpy) with alkyl halides. Methyl iodide reacts cleanly with PdMePh(tmeda) at 0 C in (CD3)2C0 to form ethane and PdIPh(tmeda), but the expected palladium(IV) intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda) below the decomposition temperature of the latter under these conditions (50 C, (CD3)2CO), while benzyl iodide reacts at 40 C to give a complicated mixture of products of which ethane, diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified. Benzyl iodide reacts with PdMe2(tmeda) at -30 C in (CD3)2CO to form PdIMe2(CH2Ph)(tmeda), for which lH NMR spectra showed the benzyl group to be trans to one of the N-donor atoms. However, PdIMe2(CH2Ph)(tmeda) is unstable and undergoes facile reductive elimination
to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium(IV) to palladium(II) complexes occurs in (CD3)2CO at low temperatures for several reaction systems in which the resulting palladium(IV) complex is known to be more stable than the
palladium(IV) reagent. There is a strong preference for benzyl group transfer from PdXMePh(CH2Ph)(bpy) to PdMe2(L2) (X = Br, I; L2 = bpy, phen). The mechanism of the transfer reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from
palladium(IV) to platinum(II), palladium(II) to palladium(O), cobalt(III) to cobalt(I), and rhodium(III) to rhodium(I). These reaction systems involve nucleophilic attack by the lower oxidation state reagent at an alkyl group attached to the higher oxidation state reagent." name="eprints.abstract" />
<meta content="1994" name="eprints.date" />
<meta content="published" name="eprints.date_type" />
<meta content="Organometallics" name="eprints.publication" />
<meta content="13" name="eprints.volume" />
<meta content="5" name="eprints.number" />
<meta content="2053-2058" name="eprints.pagerange" />
<meta content="10.1021/om00017a071" name="eprints.id_number" />
<meta content="TRUE" name="eprints.refereed" />
<meta content="0276-7333" name="eprints.issn" />
<meta content="http://dx.doi.org/10.1021/om00017a071" name="eprints.official_url" />
<meta content="
(1) (a) Byers, P. K.; Canty, A. J.; Skelton, B. W.; White, A. H. J. Chem.
Soc., Chem. Commun. 1986,1722. (b) Canty, A. J. Acc. Chem.Res. 1992,
25,83 and references therein. (c) Byers, P. K.; Canty, A. J.; Honeyman,
R. T.; Skelton, B. W.; White, A. H. J. Organomet. Chem. 1992,433,223.
(d) Canty,A. J.;Traill,P. R.;Skelton,B. W.; White,A. H. Ibid. 1992,433,
213. (e) Canty, A. J.; Traill, P. R. Ibid. 1992,435, C8. (0 Byers, P. K.;
Canty, A. J.; Skelton, B. W.; Traill, P. R.; Watson, A. A.; White, A. H.
Organometallics 1992, 11, 3085. (g) Canty, A. J. Platinum Met. Reu.
1993,37,2. (h) Bennett, M. A,; Canty, A. J.; Felixberger, J. K.; Rendina,
L. M.; Sunderland, C.; Willis, A. C. Inorg. Chem. 1993,32, 1951.
(2) (a)deGraaf,W.;Boersma,J.;Grove,D.M.;Spek.A.L.;vanKoten,
G. Recl. Trau. Chim.Pays-Bas 1988,107,299. (b) de Graaf, W.; Boersma,
J.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. Organometallics 1989,8,
2907. (c) de Graaf, W.; van Wegen, J.; Boersma, J.; Spek, A. L.; van
Koten, G. Recl. Trau. Chim. Pays-Bas 1989,108,275. (d) de Graaf, W.;
Boenma, J.; van Koten, G. Organometallics 1990,9, 1479. (e) Alsters,
P. L.; Engel, P. F.; Hogerheide, M. P.; Copijn, M.; Spek, A. L.; van Koten,
G. Ibid. 1993, 12, 1831.
(3) (a) Catellani, M.; Chiusoli, G. P. J. Organomet. Chem. 1988,346,
C27. (b) Catellani, M.; Mann, B. E. Ibid. 1990,390, 251.
(4) (a) Byers, P. K.; Canty, A. J.; Crespo, M.; Puddephatt, R. J.; Scott,
J. D. Organometallics 1988,7,1363. (b) Aye, K.-T.; Canty, A. J.; Crespo,
M.; Puddephatt, R. J.; Scott, J. D.; Watson, A. A. Ibid. 1989, 8, 1518.
(5) (a) Uson, R.; Fornies, J.; Navarro, R. J. Organomet. Chem. 1975,
96,307. (b) Uson, R.; Fornies, J.; Navarro, R. Synth. React. Inorg. Met.-
Org. Chem. 1977,7,235. (c) Uson, R.; Fornies, J. Adu. Organomet. Chem.
1988,28,219. (d) Uson, R.; Fornies, J.; Tomas, M. J. Organomet. Chem.
1988,358,525.
(6) (a)Markies,B.A.;Canty,A.J.;Janssen,M.D.;Spek,A.L.;Boersma,
J.; van Koten, G. Recl. Trao. Chim.Pays-Bas 1991,110,477. (b) Markies,
B. A.;Canty, A. J.; de Graaf, W.;Boersma, J.; Janssen,M. D.; Hogerheide,
M. P.; Smeets, W. J. J.; Spek, A. L.; van Koten, G. To be published.
(7) Byers, P. K.; Canty, A. J.; Honeyman, R. T. J. Organomet. Chem.
1990,385, 417.
(8) Byers, P. K.; Canty, A. J.; Skelton, B. W.; White, A. H. Organo-
(9) Rashidi, M.; Fakhroeian, Z.; Puddephatt, R. J. J. Organomet. Chem.
(10) Byers, P. K.; Canty, A. J.; Skelton, B. W.; Traill, P. R.; Watson,
metallics 1990, 9, 826.
1990,406, 261.
A. A.; White, A. H. Organometallics 1990, 9,3080.
(12) Monaghan, P. K.; Puddephatt, R. J. J. Chem. Soc.,Dalton Trans.
(13) Tatsumi, K.; Nakamura, A.; Komiya, S.; Yamamoto, A.; Yama-
(14) Benson, S. W. Thermochemical Kinetics, 2nd ed.; Wiley: New
1988, 595.
moto, T. J. Am. Chem. SOC. 1984, 106, 8181.
York, 1976.
(15) The Pd-aryl bond dissociation energy may, of course, be one of
these. The selective reductive elimination of toluene from PdXMe(Ph)-
(CH,Ph)(bpy) should provide an opportunityto measure the Pd-Ar bond
dissociation energy. This is currently under investigation.
(16) Milstein, D.; Stille, J. K. J. Am. Chem. SOC. 1979, 101, 4981.
(17) (a) Streitweiser, A. Solvolytic Displacement Reactions;
McGraw-Hill: New York, 1962. (b) Schrauzer, G. N.; Deutach, E. J. Am.
Chem. SOC. 1969, 91, 3341.
(18) (a) Anderson, C. M.; Puddephatt, R. J.; Ferguson, G.; Lough, A.
J. J. Chem. SOC.C, hem. Commun. 1989,1297. (b) Anderson, C. M.; Crespo,
M.; Jennings, M. C.; Lough, A. J.; Ferguson, G.; Puddephatt, R. J.
Organometallics 1991, 10, 2672. (c) Canty, A. J.; Honeyman, R. T.;
Skelton, B. W.; White, A. H. J. Organomet. Chem. 1990,389, 277.
(19) Stille, J. K.; Lau, K. S. Y. Acc. Chem. Res. 1977, 10, 434.
(20) (a) Stadlbauer, E. A.; Holland, R. J.; La", F. P.; Schrauzer, G.
N. Bioinorg. Chem. 1974,4,67. (b) Dodd, D.; Johnson, M. D.; Lockman,
B. L. J. Am. Chem. SOC. 1977, 99, 3664.
(21) Collman, J. P.; Brauman, J. I.; Madonik, A. M. Organometallics
1986, 5, 215.
(22) Coleman, G. H.; Hauser, C. R. J. Am. Chem. SOC. 1928,50,1193.
(23) Byers, P. K.; Canty, A. J. Organometallics 1990, 9, 210." name="eprints.referencetext" />
<meta content="Markies, B.A. and Canty, A.J. and Boersma, J. and van Koten, G. (1994) Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II). Organometallics, 13 (5). pp. 2053-2058. ISSN 0276-7333" name="eprints.citation" />
<meta content="http://eprints.utas.edu.au/2868/1/Organomet1994_2C_2053.pdf" name="eprints.document_url" />
<link rel="schema.DC" href="http://purl.org/DC/elements/1.0/" />
<meta content="Phenylpalladium(IV) Chemistry: Selectivity in Reductive
Elimination from Palladium(IV) Complexes and Alkyl
Halide Transfer from Palladium(IV) to Palladium(II)" name="DC.title" />
<meta content="Markies, B.A." name="DC.creator" />
<meta content="Canty, A.J." name="DC.creator" />
<meta content="Boersma, J." name="DC.creator" />
<meta content="van Koten, G." name="DC.creator" />
<meta content="259901 Organometallic Chemistry" name="DC.subject" />
<meta content="Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-bipyridyl) in acetone at 0 C to form the isolable fac-triorganopalladium(IV) complexes PdIMe2Ph(bpy) (3) and PdXMePh(CH2Ph)(bpy) [X = Br (4), I (5)]. Complex 3 occurs as a mixture of isomers in a ca. 1:l ratio, involving the phenyl group in a position trans either to bpy (3a) or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has
the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal bonded to three different groups could be studied for the first time. The complexes undergo facile reductive elimination in (CD3)2CO at 0 C, in which PdIMe2Ph(bpy) gives a mixture of ethane and toluene in a 4:l molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh(CH2Ph)(bpy) (X = Br, I) gives exclusively toluene and PdX(CH2Ph)(bpy). The analogous tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts more slowly than PdMePh(bpy) with alkyl halides. Methyl iodide reacts cleanly with PdMePh(tmeda) at 0 C in (CD3)2C0 to form ethane and PdIPh(tmeda), but the expected palladium(IV) intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda) below the decomposition temperature of the latter under these conditions (50 C, (CD3)2CO), while benzyl iodide reacts at 40 C to give a complicated mixture of products of which ethane, diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified. Benzyl iodide reacts with PdMe2(tmeda) at -30 C in (CD3)2CO to form PdIMe2(CH2Ph)(tmeda), for which lH NMR spectra showed the benzyl group to be trans to one of the N-donor atoms. However, PdIMe2(CH2Ph)(tmeda) is unstable and undergoes facile reductive elimination
to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium(IV) to palladium(II) complexes occurs in (CD3)2CO at low temperatures for several reaction systems in which the resulting palladium(IV) complex is known to be more stable than the
palladium(IV) reagent. There is a strong preference for benzyl group transfer from PdXMePh(CH2Ph)(bpy) to PdMe2(L2) (X = Br, I; L2 = bpy, phen). The mechanism of the transfer reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from
palladium(IV) to platinum(II), palladium(II) to palladium(O), cobalt(III) to cobalt(I), and rhodium(III) to rhodium(I). These reaction systems involve nucleophilic attack by the lower oxidation state reagent at an alkyl group attached to the higher oxidation state reagent." name="DC.description" />
<meta content="1994" 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/2868/1/Organomet1994_2C_2053.pdf" name="DC.identifier" />
<meta content="http://dx.doi.org/10.1021/om00017a071" name="DC.relation" />
<meta content="Markies, B.A. and Canty, A.J. and Boersma, J. and van Koten, G. (1994) Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II). Organometallics, 13 (5). pp. 2053-2058. ISSN 0276-7333" name="DC.identifier" />
<meta content="http://eprints.utas.edu.au/2868/" name="DC.relation" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/BibTeX/epprod-eprint-2868.bib" title="BibTeX" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/ContextObject/epprod-eprint-2868.xml" title="OpenURL ContextObject" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/ContextObject::Dissertation/epprod-eprint-2868.xml" title="OpenURL Dissertation" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/ContextObject::Journal/epprod-eprint-2868.xml" title="OpenURL Journal" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/DC/epprod-eprint-2868.txt" title="Dublin Core" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/DIDL/epprod-eprint-2868.xml" title="DIDL" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/EndNote/epprod-eprint-2868.enw" title="EndNote" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/HTML/epprod-eprint-2868.html" title="HTML Citation" type="text/html; charset=utf-8" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/METS/epprod-eprint-2868.xml" title="METS" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/MODS/epprod-eprint-2868.xml" title="MODS" type="text/xml" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/RIS/epprod-eprint-2868.ris" title="Reference Manager" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/Refer/epprod-eprint-2868.refer" title="Refer" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/Simple/epprod-eprint-2868text" title="Simple Metadata" type="text/plain" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/Text/epprod-eprint-2868.txt" title="ASCII Citation" type="text/plain; charset=utf-8" />
<link rel="alternate" href="http://eprints.utas.edu.au/cgi/export/2868/XML/epprod-eprint-2868.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">Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II)</h1>
<p style="margin-bottom: 1em" class="not_ep_block"><span class="person_name">Markies, B.A.</span> and <span class="person_name">Canty, A.J.</span> and <span class="person_name">Boersma, J.</span> and <span class="person_name">van Koten, G.</span> (1994) <xhtml:em>Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II).</xhtml:em> Organometallics, 13 (5). pp. 2053-2058. ISSN 0276-7333</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/2868/1/Organomet1994_2C_2053.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/2868/1/Organomet1994_2C_2053.pdf"><span class="ep_document_citation">PDF</span></a> - Full text restricted - Requires a PDF viewer<br />773Kb</td><td><form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/request_doc"><input value="4094" 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/om00017a071">http://dx.doi.org/10.1021/om00017a071</a></p><div class="not_ep_block"><h2>Abstract</h2><p style="padding-bottom: 16px; text-align: left; margin: 1em auto 0em auto">Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-bipyridyl) in acetone at 0 C to form the isolable fac-triorganopalladium(IV) complexes PdIMe2Ph(bpy) (3) and PdXMePh(CH2Ph)(bpy) [X = Br (4), I (5)]. Complex 3 occurs as a mixture of isomers in a ca. 1:l ratio, involving the phenyl group in a position trans either to bpy (3a) or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has
the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal bonded to three different groups could be studied for the first time. The complexes undergo facile reductive elimination in (CD3)2CO at 0 C, in which PdIMe2Ph(bpy) gives a mixture of ethane and toluene in a 4:l molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh(CH2Ph)(bpy) (X = Br, I) gives exclusively toluene and PdX(CH2Ph)(bpy). The analogous tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts more slowly than PdMePh(bpy) with alkyl halides. Methyl iodide reacts cleanly with PdMePh(tmeda) at 0 C in (CD3)2C0 to form ethane and PdIPh(tmeda), but the expected palladium(IV) intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda) below the decomposition temperature of the latter under these conditions (50 C, (CD3)2CO), while benzyl iodide reacts at 40 C to give a complicated mixture of products of which ethane, diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified. Benzyl iodide reacts with PdMe2(tmeda) at -30 C in (CD3)2CO to form PdIMe2(CH2Ph)(tmeda), for which lH NMR spectra showed the benzyl group to be trans to one of the N-donor atoms. However, PdIMe2(CH2Ph)(tmeda) is unstable and undergoes facile reductive elimination
to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium(IV) to palladium(II) complexes occurs in (CD3)2CO at low temperatures for several reaction systems in which the resulting palladium(IV) complex is known to be more stable than the
palladium(IV) reagent. There is a strong preference for benzyl group transfer from PdXMePh(CH2Ph)(bpy) to PdMe2(L2) (X = Br, I; L2 = bpy, phen). The mechanism of the transfer reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from
palladium(IV) to platinum(II), palladium(II) to palladium(O), cobalt(III) to cobalt(I), and rhodium(III) to rhodium(I). These reaction systems involve nucleophilic attack by the lower oxidation state reagent at an alkyl group attached to the higher oxidation state reagent.</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">ID Code:</th><td valign="top" class="ep_row">2868</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">15 Jan 2008 12:08</td></tr><tr><th valign="top" class="ep_row">Last Modified:</th><td valign="top" class="ep_row">15 Jan 2008 12:08</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=2868;">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=2868">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>
