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<title>UTas ePrints - Electrochemistry of dimeric organopalladium(II) complexes containing bridging [pyridin-2-yl(phenyl)methyl-C,N]- and [bis(pyridin-2-yl)phenylmethyl-C,N,N']- groups</title>
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<meta content="Bond, A.M." name="eprints.creators_name" />
<meta content="Canty, A.J." name="eprints.creators_name" />
<meta content="Cooper, J.B." name="eprints.creators_name" />
<meta content="Tedesco, V." name="eprints.creators_name" />
<meta content="Traill, P.R." name="eprints.creators_name" />
<meta content="Way, D.M." name="eprints.creators_name" />
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<meta content="allan.canty@utas.edu.au" name="eprints.creators_id" />
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<meta content="2008-01-31T00:46:40Z" name="eprints.datestamp" />
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<meta content="Electrochemistry of dimeric organopalladium(II) complexes
containing bridging [pyridin-2-yl(phenyl)methyl-C,N]- and
[bis(pyridin-2-yl)phenylmethyl-C,N,N']- groups" name="eprints.title" />
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<meta content="The electrochemistry of the palladium(II) dimers [Pd(CHPhpy)(L)C1]2 (L = 4-methylpyridine (4-Mepy) (la), 3,4-dimethylpyridine (3,4-Me2py) (lb), 3,5-dimethylpyridine (3,5-Me2py) (le), 2-benzylpyridine (2-Bzpy) (ld)) and [Pd(CPhpy2)Cl]2 (2) has been investigated in dichloromethane and acetonitrile. Under cyclic voltammetric conditions, complexes 1 were found to undergo acheraically reversible
one electron oxidation at moderate scan rates in dichloromethane and fast scan rates in acetonitrile. The reversible potential of this process is essentially solvent independent. A second, solvent dependent, irreversible one electron oxidation is observed at more positive potentials. In the presence of a coordinating ligand, the first oxidation becomes a two electron process on the synthetic timcscalc presumably leading to a [Pd(III)Pd(III)] dimer with a metal-metal interaction while the coordinating ligand occupies the vacant axial site on each palladium atom. Thus, long time domain electrochemical experiments occur via a different mechanism. For the formation of both one electron and two electron oxidation products, it is possible that oxidation of the ligand rather than metal centres has occurred. If Pd(III) centrcs are formed then metal-metal bond formation may occur to give bond orders of 0.5 for [Pd(III)Pd(II)]+ and 1.0 for [Pd(III)Pd(III)]2+. Complex 2 exhibits essentially the same electrochemical behaviour as complexes 1 except that the one electron oxidative product [Pd(III)Pd(II)]+ is
more stable. Thus, evidence for oxidation state + III for organopalladium complexes has been obtained, but no further oxidation to Pd(IV) was observed." name="eprints.abstract" />
<meta content="1996" name="eprints.date" />
<meta content="published" name="eprints.date_type" />
<meta content="Inorganica Chimica Acta" name="eprints.publication" />
<meta content="251" name="eprints.volume" />
<meta content="1- 2" name="eprints.number" />
<meta content="185-192" name="eprints.pagerange" />
<meta content="10.1016/S0020-1693(96)05271-1" name="eprints.id_number" />
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<meta content="Bond, A.M. and Canty, A.J. and Cooper, J.B. and Tedesco, V. and Traill, P.R. and Way, D.M. (1996) Electrochemistry of dimeric organopalladium(II) complexes containing bridging [pyridin-2-yl(phenyl)methyl-C,N]- and [bis(pyridin-2-yl)phenylmethyl-C,N,N']- groups. Inorganica Chimica Acta, 251 (1- 2). pp. 185-192. ISSN 0020-1693" name="eprints.citation" />
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<meta content="Electrochemistry of dimeric organopalladium(II) complexes
containing bridging [pyridin-2-yl(phenyl)methyl-C,N]- and
[bis(pyridin-2-yl)phenylmethyl-C,N,N']- groups" name="DC.title" />
<meta content="Bond, A.M." name="DC.creator" />
<meta content="Canty, A.J." name="DC.creator" />
<meta content="Cooper, J.B." name="DC.creator" />
<meta content="Tedesco, V." name="DC.creator" />
<meta content="Traill, P.R." name="DC.creator" />
<meta content="Way, D.M." name="DC.creator" />
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<meta content="The electrochemistry of the palladium(II) dimers [Pd(CHPhpy)(L)C1]2 (L = 4-methylpyridine (4-Mepy) (la), 3,4-dimethylpyridine (3,4-Me2py) (lb), 3,5-dimethylpyridine (3,5-Me2py) (le), 2-benzylpyridine (2-Bzpy) (ld)) and [Pd(CPhpy2)Cl]2 (2) has been investigated in dichloromethane and acetonitrile. Under cyclic voltammetric conditions, complexes 1 were found to undergo acheraically reversible
one electron oxidation at moderate scan rates in dichloromethane and fast scan rates in acetonitrile. The reversible potential of this process is essentially solvent independent. A second, solvent dependent, irreversible one electron oxidation is observed at more positive potentials. In the presence of a coordinating ligand, the first oxidation becomes a two electron process on the synthetic timcscalc presumably leading to a [Pd(III)Pd(III)] dimer with a metal-metal interaction while the coordinating ligand occupies the vacant axial site on each palladium atom. Thus, long time domain electrochemical experiments occur via a different mechanism. For the formation of both one electron and two electron oxidation products, it is possible that oxidation of the ligand rather than metal centres has occurred. If Pd(III) centrcs are formed then metal-metal bond formation may occur to give bond orders of 0.5 for [Pd(III)Pd(II)]+ and 1.0 for [Pd(III)Pd(III)]2+. Complex 2 exhibits essentially the same electrochemical behaviour as complexes 1 except that the one electron oxidative product [Pd(III)Pd(II)]+ is
more stable. Thus, evidence for oxidation state + III for organopalladium complexes has been obtained, but no further oxidation to Pd(IV) was observed." name="DC.description" />
<meta content="1996" name="DC.date" />
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<meta content="Bond, A.M. and Canty, A.J. and Cooper, J.B. and Tedesco, V. and Traill, P.R. and Way, D.M. (1996) Electrochemistry of dimeric organopalladium(II) complexes containing bridging [pyridin-2-yl(phenyl)methyl-C,N]- and [bis(pyridin-2-yl)phenylmethyl-C,N,N']- groups. Inorganica Chimica Acta, 251 (1- 2). pp. 185-192. ISSN 0020-1693" name="DC.identifier" />
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<h1 class="ep_tm_pagetitle">Electrochemistry of dimeric organopalladium(II) complexes containing bridging [pyridin-2-yl(phenyl)methyl-C,N]- and [bis(pyridin-2-yl)phenylmethyl-C,N,N']- groups</h1>
<p style="margin-bottom: 1em" class="not_ep_block"><span class="person_name">Bond, A.M.</span> and <span class="person_name">Canty, A.J.</span> and <span class="person_name">Cooper, J.B.</span> and <span class="person_name">Tedesco, V.</span> and <span class="person_name">Traill, P.R.</span> and <span class="person_name">Way, D.M.</span> (1996) <xhtml:em>Electrochemistry of dimeric organopalladium(II) complexes containing bridging [pyridin-2-yl(phenyl)methyl-C,N]- and [bis(pyridin-2-yl)phenylmethyl-C,N,N']- groups.</xhtml:em> Inorganica Chimica Acta, 251 (1- 2). pp. 185-192. ISSN 0020-1693</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/2920/1/ICA1996_2C_185.pdf"><img alt="[img]" src="http://eprints.utas.edu.au/style/images/fileicons/application_pdf.png" class="ep_doc_icon" border="0" /></a></td><td valign="top"><a href="http://eprints.utas.edu.au/2920/1/ICA1996_2C_185.pdf"><span class="ep_document_citation">PDF</span></a> - Full text restricted - Requires a PDF viewer<br />750Kb</td><td><form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/request_doc"><input accept-charset="utf-8" value="4294" name="docid" 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/10.1016/S0020-1693(96)05271-1">http://dx.doi.org/10.1016/S0020-1693(96)05271-1</a></p><div class="not_ep_block"><h2>Abstract</h2><p style="padding-bottom: 16px; text-align: left; margin: 1em auto 0em auto">The electrochemistry of the palladium(II) dimers [Pd(CHPhpy)(L)C1]2 (L = 4-methylpyridine (4-Mepy) (la), 3,4-dimethylpyridine (3,4-Me2py) (lb), 3,5-dimethylpyridine (3,5-Me2py) (le), 2-benzylpyridine (2-Bzpy) (ld)) and [Pd(CPhpy2)Cl]2 (2) has been investigated in dichloromethane and acetonitrile. Under cyclic voltammetric conditions, complexes 1 were found to undergo acheraically reversible
one electron oxidation at moderate scan rates in dichloromethane and fast scan rates in acetonitrile. The reversible potential of this process is essentially solvent independent. A second, solvent dependent, irreversible one electron oxidation is observed at more positive potentials. In the presence of a coordinating ligand, the first oxidation becomes a two electron process on the synthetic timcscalc presumably leading to a [Pd(III)Pd(III)] dimer with a metal-metal interaction while the coordinating ligand occupies the vacant axial site on each palladium atom. Thus, long time domain electrochemical experiments occur via a different mechanism. For the formation of both one electron and two electron oxidation products, it is possible that oxidation of the ligand rather than metal centres has occurred. If Pd(III) centrcs are formed then metal-metal bond formation may occur to give bond orders of 0.5 for [Pd(III)Pd(II)]+ and 1.0 for [Pd(III)Pd(III)]2+. Complex 2 exhibits essentially the same electrochemical behaviour as complexes 1 except that the one electron oxidative product [Pd(III)Pd(II)]+ is
more stable. Thus, evidence for oxidation state + III for organopalladium complexes has been obtained, but no further oxidation to Pd(IV) was observed.</p></div><table style="margin-bottom: 1em" cellpadding="3" class="not_ep_block" border="0"><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">Additional Information:</th><td valign="top" class="ep_row">The definitive version is available at http://www.sciencedirect.com
</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">2920</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">31 Jan 2008 11:46</td></tr><tr><th valign="top" class="ep_row">Last Modified:</th><td valign="top" class="ep_row">31 Jan 2008 11:46</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=2920;">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=2920">item control page</a></p>
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