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<title>UTas ePrints - Volume Profile Analysis of Oxidative Addition to Palladium(II) and Reductive Elimination from Palladium(IV)</title>
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<meta content="Ducker-Benfer, C." name="eprints.creators_name" />
<meta content="van Eldik, R." name="eprints.creators_name" />
<meta content="Canty, A.J." name="eprints.creators_name" />
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<meta content="The oxidative addition of MeI to Pd(II) in the complex PdMe2(bpy) to produce PdIMe3(bpy) was studied as a function of [MeI] and pressure. The DV* of -11.9 +/- 0.6 cm3 mol-' for the addition process underlines the validity of the proposed SN2 mechanism in the literature. The
reductive elimination from PdIMe3(bpy) to form PdIMe(bpy) and C2H6 was studied as a function of pressure and [NaI]. The complex was prepared in situ via oxidative addition of Me1 to the Pd(II) complex. DV* is +17 +/- 1 cm3/mol for the reductive elimination process. If NaI is added
to the Pd(IV) compound, the rate slows down, but it did not affect the activation volume. The large positive value of DV* for the elimination reaction suggests bond cleavage and/or the partial reduction from Pd(IV) to Pd(II) in the transition state. A volume profile for the overall oxidative addition and reductive elimination reactions is presented." name="eprints.abstract" />
<meta content="1994" name="eprints.date" />
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<meta content="The oxidative addition of MeI to Pd(II) in the complex PdMe2(bpy) to produce PdIMe3(bpy) was studied as a function of [MeI] and pressure. The DV* of -11.9 +/- 0.6 cm3 mol-' for the addition process underlines the validity of the proposed SN2 mechanism in the literature. The
reductive elimination from PdIMe3(bpy) to form PdIMe(bpy) and C2H6 was studied as a function of pressure and [NaI]. The complex was prepared in situ via oxidative addition of Me1 to the Pd(II) complex. DV* is +17 +/- 1 cm3/mol for the reductive elimination process. If NaI is added
to the Pd(IV) compound, the rate slows down, but it did not affect the activation volume. The large positive value of DV* for the elimination reaction suggests bond cleavage and/or the partial reduction from Pd(IV) to Pd(II) in the transition state. A volume profile for the overall oxidative addition and reductive elimination reactions is presented." name="DC.description" />
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<h1 class="ep_tm_pagetitle">Volume Profile Analysis of Oxidative Addition to Palladium(II) and Reductive Elimination from Palladium(IV)</h1>
<p style="margin-bottom: 1em" class="not_ep_block"><span class="person_name">Ducker-Benfer, C.</span> and <span class="person_name">van Eldik, R.</span> and <span class="person_name">Canty, A.J.</span> (1994) <xhtml:em>Volume Profile Analysis of Oxidative Addition to Palladium(II) and Reductive Elimination from Palladium(IV).</xhtml:em> Organometallics, 13 (6). pp. 2412-2414. 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/2910/1/Organomet1994_2C__2412.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/2910/1/Organomet1994_2C__2412.pdf"><span class="ep_document_citation">PDF</span></a> - Full text restricted - Requires a PDF viewer<br />358Kb</td><td><form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/request_doc"><input value="4279" 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/om00018a038">http://dx.doi.org/10.1021/om00018a038</a></p><div class="not_ep_block"><h2>Abstract</h2><p style="padding-bottom: 16px; text-align: left; margin: 1em auto 0em auto">The oxidative addition of MeI to Pd(II) in the complex PdMe2(bpy) to produce PdIMe3(bpy) was studied as a function of [MeI] and pressure. The DV* of -11.9 +/- 0.6 cm3 mol-' for the addition process underlines the validity of the proposed SN2 mechanism in the literature. The
reductive elimination from PdIMe3(bpy) to form PdIMe(bpy) and C2H6 was studied as a function of pressure and [NaI]. The complex was prepared in situ via oxidative addition of Me1 to the Pd(II) complex. DV* is +17 +/- 1 cm3/mol for the reductive elimination process. If NaI is added
to the Pd(IV) compound, the rate slows down, but it did not affect the activation volume. The large positive value of DV* for the elimination reaction suggests bond cleavage and/or the partial reduction from Pd(IV) to Pd(II) in the transition state. A volume profile for the overall oxidative addition and reductive elimination reactions is presented.</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">2910</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">30 Jan 2008 14:48</td></tr><tr><th valign="top" class="ep_row">Last Modified:</th><td valign="top" class="ep_row">30 Jan 2008 14:48</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=2910;">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=2910">item control page</a></p>
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