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<meta content="Canty, A.J." name="eprints.creators_name" />
<meta content="Denney, M.C." name="eprints.creators_name" />
<meta content="Patel, J." name="eprints.creators_name" />
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<meta content="Skelton, B.W." name="eprints.creators_name" />
<meta content="White, A.H." name="eprints.creators_name" />
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<meta content="Reversible oxidative addition of a diaryl diselenide to a
diorganopalladium(II) complex, carbon–selenium bond formation at palladium(IV), and structural studies of palladium(II) and platinum(IV) selenolates" name="eprints.title" />
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<meta content="Methyl(4-methoxyphenyl)(2,2'-bipyridine)palladium(II) (1) reacts with bis(4-chlorophenyl) diselenide in dichloromethane to form an equilibrium with the Pd(IV) complex Pd(SeC6H4Cl)2Me(C6H4OMe)(bpy) (2) for which the forward reaction exhibits DH = -130 +/- 12 kJ mol-1 and DS = -472 +/- 49 JK-1 mol-1, and with K = 754 +/- 145 at -25 C. The Pd(IV) complex is isolable at -40 C, and when the equilibrium mixture is kept at -25 C, a temperature at which the Pd(II) complex is stable, selective reductive
elimination of Me–SeC6H4Cl occurs very slowly from the Pd(IV) complex to form Pd(SeC6H4Cl)(C6H4OMe)(bpy) (3). In contrast, (ClC6H4Se)2 reacts with PdMe2(dmpe) (4) [dmpe = 1,2-bis(dimethylphosphino)ethane] to form Pd(SeC6H4Cl)Me(dmpe) (5) and Me–SeC6H4Cl. A second equivalent of (ClC6H4Se)2 reacts with 5 to cleave the second Pd–Me bond to give Pd(SeC6H4Cl)2(dmpe) (6) and Me–SeC6H4Cl. Similarly, PdMeTol(dmpe) (7) (Tol = 4-tolyl) forms predominantly Pd(SeC6H4Cl)Tol(dmpe) (8) together
with some Pd(SeC6H4Cl)Me(dmpe) (5), and 8 reacts with (ClC6H4Se)2 to form Pd(SeC6H4Cl)2(dmpe) (6) and Tol-SeC6H4Cl. Bis(4-chlorophenyl) diselenide reacts with PtTol2(bpy) (9) (Tol = 4-tolyl) to form Pt(SeC6H4Cl)2Tol2(bpy) (10) which, together with 2, has a trans-configuration for the selenolate ligands. X-ray structural studies of octahedral 10 as the solvate 10.3CHCl3 and square
planar 5 are reported." name="eprints.abstract" />
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<meta content="[1] P.M. Henry, J. Org. Chem. 36 (1971) 1886.
[2] L.M. Stock, K.-t. Tse, L.J. Vorvick, S.A. Walstrum, J. Org.
Chem. 46 (1981) 1757.
[3] T. Yoneyama, R.H. Crabtree, J. Mol. Catal. A 108 (1996)
35.
[4] A.J. Canty, M.C. Done, B.W. Skelton, A.H. White, Inorg. Chem.
Commun. 4 (2001) 648.
[5] A.J. Canty, H. Jin, B.W. Skelton, A.H. White, Inorg. Chem. 37
(1998) 3975.
[6] A. Panunzi, G. Roviello, F. Ruffo, Organometallics 21 (2002)
3503.
[7] D. Kruis, B.A. Markies, A.J. Canty, J. Boersma, G. van Koten, J.
Organomet. Chem. 532 (1997) 235.
[8] W. de Graaf, J. Boersma, W.J.J. Smeets, A.L. Spek, G. van
Koten, Organometallics 8 (1989) 2907.
[9] M.A. Casado Lacabra, A.J. Canty, M. Lutz, J. Patel, A.L. Spek,
H. Sun, G. van Koten, Inorg. Chim. Acta 327 (2002) 15.
[10] S.R. Hall, D.J. Du Boulay, R. Olthof-Hazekamp (Eds.), The
XTAL 3.7 System, University of Western Australia, 2001.
[11] T. Spaniel, H. Schmidt, C. Wagner, K. Merzweiler, D. Steinborn,
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[12] A. Singhal, V.K. Jain, B. Varghese, E.R.T. Tiekink, Inorg. Chim.
Acta 285 (1999) 190." name="eprints.referencetext" />
<meta content="Canty, A.J. and Denney, M.C. and Patel, J. and Sun, H. and Skelton, B.W. and White, A.H. (2004) Reversible oxidative addition of a diaryl diselenide to a diorganopalladium(II) complex, carbon–selenium bond formation at palladium(IV), and structural studies of palladium(II) and platinum(IV) selenolates. Journal of Organometallic Chemistry, 689 (3). pp. 672-677. ISSN 0022-328X" name="eprints.citation" />
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<meta content="Methyl(4-methoxyphenyl)(2,2'-bipyridine)palladium(II) (1) reacts with bis(4-chlorophenyl) diselenide in dichloromethane to form an equilibrium with the Pd(IV) complex Pd(SeC6H4Cl)2Me(C6H4OMe)(bpy) (2) for which the forward reaction exhibits DH = -130 +/- 12 kJ mol-1 and DS = -472 +/- 49 JK-1 mol-1, and with K = 754 +/- 145 at -25 C. The Pd(IV) complex is isolable at -40 C, and when the equilibrium mixture is kept at -25 C, a temperature at which the Pd(II) complex is stable, selective reductive
elimination of Me–SeC6H4Cl occurs very slowly from the Pd(IV) complex to form Pd(SeC6H4Cl)(C6H4OMe)(bpy) (3). In contrast, (ClC6H4Se)2 reacts with PdMe2(dmpe) (4) [dmpe = 1,2-bis(dimethylphosphino)ethane] to form Pd(SeC6H4Cl)Me(dmpe) (5) and Me–SeC6H4Cl. A second equivalent of (ClC6H4Se)2 reacts with 5 to cleave the second Pd–Me bond to give Pd(SeC6H4Cl)2(dmpe) (6) and Me–SeC6H4Cl. Similarly, PdMeTol(dmpe) (7) (Tol = 4-tolyl) forms predominantly Pd(SeC6H4Cl)Tol(dmpe) (8) together
with some Pd(SeC6H4Cl)Me(dmpe) (5), and 8 reacts with (ClC6H4Se)2 to form Pd(SeC6H4Cl)2(dmpe) (6) and Tol-SeC6H4Cl. Bis(4-chlorophenyl) diselenide reacts with PtTol2(bpy) (9) (Tol = 4-tolyl) to form Pt(SeC6H4Cl)2Tol2(bpy) (10) which, together with 2, has a trans-configuration for the selenolate ligands. X-ray structural studies of octahedral 10 as the solvate 10.3CHCl3 and square
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<h1 class="ep_tm_pagetitle">Reversible oxidative addition of a diaryl diselenide to a diorganopalladium(II) complex, carbon–selenium bond formation at palladium(IV), and structural studies of palladium(II) and platinum(IV) selenolates</h1>
<p style="margin-bottom: 1em" class="not_ep_block"><span class="person_name">Canty, A.J.</span> and <span class="person_name">Denney, M.C.</span> and <span class="person_name">Patel, J.</span> and <span class="person_name">Sun, H.</span> and <span class="person_name">Skelton, B.W.</span> and <span class="person_name">White, A.H.</span> (2004) <xhtml:em>Reversible oxidative addition of a diaryl diselenide to a diorganopalladium(II) complex, carbon–selenium bond formation at palladium(IV), and structural studies of palladium(II) and platinum(IV) selenolates.</xhtml:em> Journal of Organometallic Chemistry, 689 (3). pp. 672-677. ISSN 0022-328X</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/2809/1/JOMC_2C_689_2C_672.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/2809/1/JOMC_2C_689_2C_672.pdf"><span class="ep_document_citation">PDF</span></a> - Full text restricted - Requires a PDF viewer<br />229Kb</td><td><form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/request_doc"><input accept-charset="utf-8" value="3834" 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/j.jorganchem.2003.12.010">http://dx.doi.org/10.1016/j.jorganchem.2003.12.010</a></p><div class="not_ep_block"><h2>Abstract</h2><p style="padding-bottom: 16px; text-align: left; margin: 1em auto 0em auto">Methyl(4-methoxyphenyl)(2,2'-bipyridine)palladium(II) (1) reacts with bis(4-chlorophenyl) diselenide in dichloromethane to form an equilibrium with the Pd(IV) complex Pd(SeC6H4Cl)2Me(C6H4OMe)(bpy) (2) for which the forward reaction exhibits DH = -130 +/- 12 kJ mol-1 and DS = -472 +/- 49 JK-1 mol-1, and with K = 754 +/- 145 at -25 C. The Pd(IV) complex is isolable at -40 C, and when the equilibrium mixture is kept at -25 C, a temperature at which the Pd(II) complex is stable, selective reductive
elimination of Me–SeC6H4Cl occurs very slowly from the Pd(IV) complex to form Pd(SeC6H4Cl)(C6H4OMe)(bpy) (3). In contrast, (ClC6H4Se)2 reacts with PdMe2(dmpe) (4) [dmpe = 1,2-bis(dimethylphosphino)ethane] to form Pd(SeC6H4Cl)Me(dmpe) (5) and Me–SeC6H4Cl. A second equivalent of (ClC6H4Se)2 reacts with 5 to cleave the second Pd–Me bond to give Pd(SeC6H4Cl)2(dmpe) (6) and Me–SeC6H4Cl. Similarly, PdMeTol(dmpe) (7) (Tol = 4-tolyl) forms predominantly Pd(SeC6H4Cl)Tol(dmpe) (8) together
with some Pd(SeC6H4Cl)Me(dmpe) (5), and 8 reacts with (ClC6H4Se)2 to form Pd(SeC6H4Cl)2(dmpe) (6) and Tol-SeC6H4Cl. Bis(4-chlorophenyl) diselenide reacts with PtTol2(bpy) (9) (Tol = 4-tolyl) to form Pt(SeC6H4Cl)2Tol2(bpy) (10) which, together with 2, has a trans-configuration for the selenolate ligands. X-ray structural studies of octahedral 10 as the solvate 10.3CHCl3 and square
planar 5 are reported.</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">ID Code:</th><td valign="top" class="ep_row">2809</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">04 Jan 2008 12:53</td></tr><tr><th valign="top" class="ep_row">Last Modified:</th><td valign="top" class="ep_row">09 Jan 2008 02:30</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=2809;">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=2809">item control page</a></p>
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