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<meta content="Phenacyl bromides react with dimethylpalladium(II) complexes PdMe2(L2) (L2 = bpy, phen) to form the palladium(IV) complexes fac-PdBrMe2(CH2COAr)(L2) (Ar = Ph, p-C6H4Br), which have both methyl groups trans to the bidentate nitrogen donor ligand. 1H NMR studies of the oxidative addition of phenacyl bromides to PdMe2(bpy) in (CD3)2C0 at -5 C indicate the formation of two similar cationic intermediates, prior to formation of the neutral product. As the cations have only one of the methyl groups trans to bpy, configurational changes at palladium occur on cation formation and on conversion of the cations to the
neutral product. It is proposed that one of the cations may be stabilized via an intramolecularly coordinated
phenacyl group, [PdMe2(CH2COAr-C,0)(L2)]+. A single cation, exhibiting NMR spectra similar to those
of the cations of the bpy complexes, is detected as an intermediate in the reaction of PdMe2(phen) with
ArCOCH2Br. A cation has also been detected for the reaction of PdMe2(bpy) with CD3I in (CD3)2C0 at -50 C, prior to formation of PdIMe2(CD3)(bpy). Both the cation, most likely [PdMe2(CD3)(bpy)((CD3)2CO)]+, and the neutral product display scrambled Me and CD3 groups, in contrast to the trans oxidative addition reported for the analogous reaction of PtMe2(bpy) with CD3I. Crystals of PdBrMe2-
(CH2COAr)(bpy) are orthorhombic, space group Pbca, with a = 19.554 (3) A, b = 15.007 (9) A, c = 13.282(4) A, and Z = 8." name="eprints.abstract" />
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(1) (a) University of Tasmania. (b) Present address: School of
Chemistry, The University of Birmingham, Birmingham B15 2TT,
England. (c) University of Western Australia.
(2) Chock, P. B.; Halpern, J. J. Am. Chem. SOC. 1966,88,3511.
(3) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles
and Applications of Organotransition Metal Chemistry; University
Science Books: Mill Valley, CA, 1987; Chapter 5.
(4) Puddephatt, R. J.; Scott, J. D. Organometallics 1986, 4, 1221.
(5) Creepo, M.; Puddephatt, R. J. Organometallics 1987, 6, 2548.
(6) Byers, P. K.; Canty, A. J.; Skelton, B. W.; White, A. H. J. Chem.
SOC.C, hem. Commun. 1986,1722.
(7) Canty, A. J. Acc. Chem. Res. 1992,25, 83.
(8) (a) de Graaf, W.; Boerema, J.; Smeets, W. J. J.; Spek, A. L.; van
Kotan, G. Organometallics 1989,8,2907. (b) de Graaf, W.; Boerama, J.;
van Koten, G. Organometallics 1990, 9, 1479.
(9) Catellani, M.; Chiusoli, G. P. J. Orgammet. Chem. 1988,346, C27.
Catellani, M.; Mann, B. E. J. Organomet. Chem. 1990,390, 251.
(10) (a) Byera, PYK.; CanG, A. J.; Creapo, MI; Puddephstt, R. J.; Scott,
J. D. Organometallics 1988, 7,1363. (b) Aye, K.-T.; Canty, A. J.; Creapo,
M.; Puddephatt, R. J.; Scott, J. D.; Watson, A. A. Organometallics 1989,
8, 1518.
(11) Canty, A. J.; Watson, A. A.; Skelton, B. W.; White, A. H. J.
Organomet. Chem. 1989,367, C25.
(12) Byere, P. K.; Canty, A. J.; Skelton,BTW.;T raill, P. R.; Watson,
A. A.; White, A. H. Organometallics 1990,9,3080.
(13) Byers, P. K.; Canty, A. J. Organometallics 1990, 9, 210.
(14) Ibers, J. A., Hamilton, W. C., Eds. Internotional Tables for XRay
Crystallography; Kynoch Press: Birmingham, England, 1974; Vol.
4.
(15) 9 S. R.; Stewart, J. M. The XTAL User's ManwbVerawn 3.0;
University of Western Austrdi, Nedlands, Australia, and University of
Maryland, College Park, MD, 1990." name="eprints.referencetext" />
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<meta content="Phenacyl bromides react with dimethylpalladium(II) complexes PdMe2(L2) (L2 = bpy, phen) to form the palladium(IV) complexes fac-PdBrMe2(CH2COAr)(L2) (Ar = Ph, p-C6H4Br), which have both methyl groups trans to the bidentate nitrogen donor ligand. 1H NMR studies of the oxidative addition of phenacyl bromides to PdMe2(bpy) in (CD3)2C0 at -5 C indicate the formation of two similar cationic intermediates, prior to formation of the neutral product. As the cations have only one of the methyl groups trans to bpy, configurational changes at palladium occur on cation formation and on conversion of the cations to the
neutral product. It is proposed that one of the cations may be stabilized via an intramolecularly coordinated
phenacyl group, [PdMe2(CH2COAr-C,0)(L2)]+. A single cation, exhibiting NMR spectra similar to those
of the cations of the bpy complexes, is detected as an intermediate in the reaction of PdMe2(phen) with
ArCOCH2Br. A cation has also been detected for the reaction of PdMe2(bpy) with CD3I in (CD3)2C0 at -50 C, prior to formation of PdIMe2(CD3)(bpy). Both the cation, most likely [PdMe2(CD3)(bpy)((CD3)2CO)]+, and the neutral product display scrambled Me and CD3 groups, in contrast to the trans oxidative addition reported for the analogous reaction of PtMe2(bpy) with CD3I. Crystals of PdBrMe2-
(CH2COAr)(bpy) are orthorhombic, space group Pbca, with a = 19.554 (3) A, b = 15.007 (9) A, c = 13.282(4) A, and Z = 8." name="DC.description" />
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<h1 class="ep_tm_pagetitle">1H NMR Detection of Cationic Organopalladium(IV) Intermediates in Oxidative-Addition Reactions and the Structure of fac-PdBrMe2(CH2COPh)(bpy)</h1>
<p style="margin-bottom: 1em" class="not_ep_block"><span class="person_name">Byers, P.K.</span> and <span class="person_name">Canty, A.J.</span> and <span class="person_name">Skelton, B.W.</span> and <span class="person_name">Traill, P.R.</span> and <span class="person_name">Watson, A.A.</span> and <span class="person_name">White, A.H.</span> (1992) <xhtml:em>1H NMR Detection of Cationic Organopalladium(IV) Intermediates in Oxidative-Addition Reactions and the Structure of fac-PdBrMe2(CH2COPh)(bpy).</xhtml:em> Organometallics, 11 (9). pp. 3085-3088. 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/2870/1/Organomet1992_2C_3085.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/2870/1/Organomet1992_2C_3085.pdf"><span class="ep_document_citation">PDF</span></a> - Full text restricted - Requires a PDF viewer<br />498Kb</td><td><form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/request_doc"><input value="4097" 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/om00045a023">http://dx.doi.org/10.1021/om00045a023</a></p><div class="not_ep_block"><h2>Abstract</h2><p style="padding-bottom: 16px; text-align: left; margin: 1em auto 0em auto">Phenacyl bromides react with dimethylpalladium(II) complexes PdMe2(L2) (L2 = bpy, phen) to form the palladium(IV) complexes fac-PdBrMe2(CH2COAr)(L2) (Ar = Ph, p-C6H4Br), which have both methyl groups trans to the bidentate nitrogen donor ligand. 1H NMR studies of the oxidative addition of phenacyl bromides to PdMe2(bpy) in (CD3)2C0 at -5 C indicate the formation of two similar cationic intermediates, prior to formation of the neutral product. As the cations have only one of the methyl groups trans to bpy, configurational changes at palladium occur on cation formation and on conversion of the cations to the
neutral product. It is proposed that one of the cations may be stabilized via an intramolecularly coordinated
phenacyl group, [PdMe2(CH2COAr-C,0)(L2)]+. A single cation, exhibiting NMR spectra similar to those
of the cations of the bpy complexes, is detected as an intermediate in the reaction of PdMe2(phen) with
ArCOCH2Br. A cation has also been detected for the reaction of PdMe2(bpy) with CD3I in (CD3)2C0 at -50 C, prior to formation of PdIMe2(CD3)(bpy). Both the cation, most likely [PdMe2(CD3)(bpy)((CD3)2CO)]+, and the neutral product display scrambled Me and CD3 groups, in contrast to the trans oxidative addition reported for the analogous reaction of PtMe2(bpy) with CD3I. Crystals of PdBrMe2-
(CH2COAr)(bpy) are orthorhombic, space group Pbca, with a = 19.554 (3) A, b = 15.007 (9) A, c = 13.282(4) A, and Z = 8.</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">2870</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 13:22</td></tr><tr><th valign="top" class="ep_row">Last Modified:</th><td valign="top" class="ep_row">15 Jan 2008 13:22</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=2870;">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=2870">item control page</a></p>
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