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<title>UTas ePrints - Organoplatinum(IV) and Palladium(IV) Complexes Containing Intramolecular Coordination Systems Based on the 8-Methylquinolinyl Group (mq), Including Structures of the Cation [Pt(mq)Me2(bpy)]+ (bpy = 2,2'-bipyridine) and the Palladium(IV) Complexes Pd(mq)MeR{(pz)2BH2} (R = Me, Ph; [(pz)2BH2]- = Bis(pyrazol-1-yl)borate)</title>
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<meta content="Canty, A.J." name="eprints.creators_name" />
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<meta content="Organoplatinum(IV) and Palladium(IV) Complexes Containing Intramolecular Coordination Systems Based on the 8-Methylquinolinyl Group (mq), Including Structures of the Cation [Pt(mq)Me2(bpy)]+ (bpy = 2,2'-bipyridine) and the Palladium(IV) Complexes Pd(mq)MeR{(pz)2BH2} (R = Me, Ph; [(pz)2BH2]- = Bis(pyrazol-1-yl)borate)" name="eprints.title" />
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<meta content="Oxidative addition of 8-(bromomethyl)quinoline (mqBr) to PdMeR(bpy) (R = Me, Ph; bpy = 2,2'-bipyridine) and [PdMeR{(pz)2BH2}]- (R = Me, Ph; [(pz)2BH2]- = bis(pyrazol-1-yl)borate]) has given the first isolable palladium(IV) complexes containing an intramolecular coordination system, [Pd(mq)MeR(bpy)]Br [R = Me (1), Ph (2)] and [Pd(mq)MeR{(pz)2BH2}- [R = Me (7), Ph (8)]. The pallada(IV)cyclic complex [Pd(CH2CH2CH2CH2)(mq)(bpy)]Br (6) has also been isolated. The first structural analysis of an arylpalladium(IV) complex, Pd(mq)MePh{(pz)2BH2} (8), is reported. Complex 8 occurs as two isomers and the one examined
by X-ray crystallography has the fac-PdC3 configuration with the phenyl group trans to the quinoline nitrogen donor. NMR spectra of 8 indicate that the other isomer has the methyl group trans to the quinoline nitrogen donor. Similar geometric isomerism occurs for [Pd(mq)MePh(bpy)]BF4 (4). Structural studies of the dimethylpalladium(IV) complex Pd(mq)Me2{(pz)2BH2} (7) and the platinum(IV) cation in [Pt(mq)Me2(bpy)]BF4.0.75(CH2Cl2) (5) reveal
similar structures. The cation [Pd(mq)Me2(bpy)]+ is less stable than the methyl(phenyl)palladium(IV) analogue (2), decomposing in (CD3)2CO by reductive elimination to form ethane and 8-ethylquinoline in ~1:2 ratio, together with the Pd(II) products [Pd(mq)(bpy)]Br and PdBrMe(bpy). A complex mixture of 8-substituted-quinolines (saturated and unsaturated substituents) were obtained as the major products of decomposition of [Pd(CH2CH2CH2CH2)(mq)(bpy)]Br (6), consistent with mq...CH2 coupling to give Pd(II) species that undergo further decomposition." name="eprints.abstract" />
<meta content="1999" name="eprints.date" />
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<meta content="Organometallics" name="eprints.publication" />
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<meta content="14" name="eprints.number" />
<meta content="2660-2667" name="eprints.pagerange" />
<meta content="10.1021/om99010k" name="eprints.id_number" />
<meta content="TRUE" name="eprints.refereed" />
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Scheme 1. Synthesis of Complexes
[Pd(mq)Me2(bpy)]Br f 0.35 {Me-Me +
[Pd(mq)(bpy)]Br} + 0.65 {Me-mq + PdBrMe(bpy)}
(1)
Scheme 2. Reductive Elimination
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Catal. A 1996, 108, 35. (c) Canty, A. J.; Jin, H.; Skelton, B. W.; White,
A. H. Inorg. Chem. 1998, 37, 3975." name="eprints.referencetext" />
<meta content="Canty, A.J. and Hoare, J.L. and Patel, J. and Pfeffer, M. and Skelton, B.W. and White, A.H. (1999) Organoplatinum(IV) and Palladium(IV) Complexes Containing Intramolecular Coordination Systems Based on the 8-Methylquinolinyl Group (mq), Including Structures of the Cation [Pt(mq)Me2(bpy)]+ (bpy = 2,2'-bipyridine) and the Palladium(IV) Complexes Pd(mq)MeR{(pz)2BH2} (R = Me, Ph; [(pz)2BH2]- = Bis(pyrazol-1-yl)borate). Organometallics, 18 (14). pp. 2660-2667. ISSN 0276-7333" name="eprints.citation" />
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<meta content="Canty, A.J." name="DC.creator" />
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<meta content="Oxidative addition of 8-(bromomethyl)quinoline (mqBr) to PdMeR(bpy) (R = Me, Ph; bpy = 2,2'-bipyridine) and [PdMeR{(pz)2BH2}]- (R = Me, Ph; [(pz)2BH2]- = bis(pyrazol-1-yl)borate]) has given the first isolable palladium(IV) complexes containing an intramolecular coordination system, [Pd(mq)MeR(bpy)]Br [R = Me (1), Ph (2)] and [Pd(mq)MeR{(pz)2BH2}- [R = Me (7), Ph (8)]. The pallada(IV)cyclic complex [Pd(CH2CH2CH2CH2)(mq)(bpy)]Br (6) has also been isolated. The first structural analysis of an arylpalladium(IV) complex, Pd(mq)MePh{(pz)2BH2} (8), is reported. Complex 8 occurs as two isomers and the one examined
by X-ray crystallography has the fac-PdC3 configuration with the phenyl group trans to the quinoline nitrogen donor. NMR spectra of 8 indicate that the other isomer has the methyl group trans to the quinoline nitrogen donor. Similar geometric isomerism occurs for [Pd(mq)MePh(bpy)]BF4 (4). Structural studies of the dimethylpalladium(IV) complex Pd(mq)Me2{(pz)2BH2} (7) and the platinum(IV) cation in [Pt(mq)Me2(bpy)]BF4.0.75(CH2Cl2) (5) reveal
similar structures. The cation [Pd(mq)Me2(bpy)]+ is less stable than the methyl(phenyl)palladium(IV) analogue (2), decomposing in (CD3)2CO by reductive elimination to form ethane and 8-ethylquinoline in ~1:2 ratio, together with the Pd(II) products [Pd(mq)(bpy)]Br and PdBrMe(bpy). A complex mixture of 8-substituted-quinolines (saturated and unsaturated substituents) were obtained as the major products of decomposition of [Pd(CH2CH2CH2CH2)(mq)(bpy)]Br (6), consistent with mq...CH2 coupling to give Pd(II) species that undergo further decomposition." name="DC.description" />
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<h1 class="ep_tm_pagetitle">Organoplatinum(IV) and Palladium(IV) Complexes Containing Intramolecular Coordination Systems Based on the 8-Methylquinolinyl Group (mq), Including Structures of the Cation [Pt(mq)Me2(bpy)]+ (bpy = 2,2'-bipyridine) and the Palladium(IV) Complexes Pd(mq)MeR{(pz)2BH2} (R = Me, Ph; [(pz)2BH2]- = Bis(pyrazol-1-yl)borate)</h1>
<p style="margin-bottom: 1em" class="not_ep_block"><span class="person_name">Canty, A.J.</span> and <span class="person_name">Hoare, J.L.</span> and <span class="person_name">Patel, J.</span> and <span class="person_name">Pfeffer, M.</span> and <span class="person_name">Skelton, B.W.</span> and <span class="person_name">White, A.H.</span> (1999) <xhtml:em>Organoplatinum(IV) and Palladium(IV) Complexes Containing Intramolecular Coordination Systems Based on the 8-Methylquinolinyl Group (mq), Including Structures of the Cation [Pt(mq)Me2(bpy)]+ (bpy = 2,2'-bipyridine) and the Palladium(IV) Complexes Pd(mq)MeR{(pz)2BH2} (R = Me, Ph; [(pz)2BH2]- = Bis(pyrazol-1-yl)borate).</xhtml:em> Organometallics, 18 (14). pp. 2660-2667. 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/2884/1/Organomet1999_2C_2660.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/2884/1/Organomet1999_2C_2660.pdf"><span class="ep_document_citation">PDF</span></a> - Full text restricted - Requires a PDF viewer<br />158Kb</td><td><form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/request_doc"><input value="4138" 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/om990130k">http://dx.doi.org/10.1021/om990130k</a></p><div class="not_ep_block"><h2>Abstract</h2><p style="padding-bottom: 16px; text-align: left; margin: 1em auto 0em auto">Oxidative addition of 8-(bromomethyl)quinoline (mqBr) to PdMeR(bpy) (R = Me, Ph; bpy = 2,2'-bipyridine) and [PdMeR{(pz)2BH2}]- (R = Me, Ph; [(pz)2BH2]- = bis(pyrazol-1-yl)borate]) has given the first isolable palladium(IV) complexes containing an intramolecular coordination system, [Pd(mq)MeR(bpy)]Br [R = Me (1), Ph (2)] and [Pd(mq)MeR{(pz)2BH2}- [R = Me (7), Ph (8)]. The pallada(IV)cyclic complex [Pd(CH2CH2CH2CH2)(mq)(bpy)]Br (6) has also been isolated. The first structural analysis of an arylpalladium(IV) complex, Pd(mq)MePh{(pz)2BH2} (8), is reported. Complex 8 occurs as two isomers and the one examined
by X-ray crystallography has the fac-PdC3 configuration with the phenyl group trans to the quinoline nitrogen donor. NMR spectra of 8 indicate that the other isomer has the methyl group trans to the quinoline nitrogen donor. Similar geometric isomerism occurs for [Pd(mq)MePh(bpy)]BF4 (4). Structural studies of the dimethylpalladium(IV) complex Pd(mq)Me2{(pz)2BH2} (7) and the platinum(IV) cation in [Pt(mq)Me2(bpy)]BF4.0.75(CH2Cl2) (5) reveal
similar structures. The cation [Pd(mq)Me2(bpy)]+ is less stable than the methyl(phenyl)palladium(IV) analogue (2), decomposing in (CD3)2CO by reductive elimination to form ethane and 8-ethylquinoline in ~1:2 ratio, together with the Pd(II) products [Pd(mq)(bpy)]Br and PdBrMe(bpy). A complex mixture of 8-substituted-quinolines (saturated and unsaturated substituents) were obtained as the major products of decomposition of [Pd(CH2CH2CH2CH2)(mq)(bpy)]Br (6), consistent with mq...CH2 coupling to give Pd(II) species that undergo further decomposition.</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">2884</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">16 Jan 2008 14:22</td></tr><tr><th valign="top" class="ep_row">Last Modified:</th><td valign="top" class="ep_row">16 Jan 2008 14:34</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=2884;">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=2884">item control page</a></p>
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