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<meta content="Aye, K.-H." name="eprints.creators_name" />
<meta content="Canty, A.J." name="eprints.creators_name" />
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<meta content="Kinetic studies of the oxidative addition of MeI or PhCH2Br to [MMe2(L2)] (M = Pd or Pt, L2 =
2,2'-bipyridine or 1,lO-phenanthroline) indicate that the reactions occur by the SN2 mechanism, and the reactions occur 7-22 times faster when M = Pt over Pd and 1.2-2.2 times faster when L2 = phen over bpy. Reductive elimination from [PdBrMe2(CH2Ph)(L2)] in the solid state occurs to give both Me-Me and PhCH2Me, and there is a preference for methyl group loss. Thermochemical studies indicate that CH3-CH3 loss gives DH = -108 +/- 4 kJ mol-' but PhCH2-CH3 loss gives DH = -48 +/- 12 kJ mol-', indicating a relatively strong PhCH2-Pd bond. The complexes [PdIMe3(L2)] or [PdBrMe2(CH2Ph)(L2)] react rapidly with [PtMe2(L2)] by alkyl halide transfer. Kinetic studies have shown that the major route involves loss of halide from palladium(IV) in a preequilibrium step, followed by SN2 attack by [PtMe2(L2)] on an alkyl group
of [PdMe3(L2)]+ or [PdMe2(CH2Ph)(L2)]+. In the latter case, benzyl group transfer is preferred over methyl
group transfer." name="eprints.abstract" />
<meta content="1989" name="eprints.date" />
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<meta content="Organometallics" name="eprints.publication" />
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(1) (a) University of Western Ontario. (b) University of Tasmania. (c)
Present address: Department of chemistry, University of Barcelona,
08028 Barcelona, Spain. (d) 3M Canada.
(2) Byers, P. K.; Canty, A. J.; Skelton, B. W.; White, A. H. J. Chem.
SOC.C, hem. Commun. 1986, 1722.
(3) Byers, P. K.; Canty, A. J.; Skelton, B. W.; White, A. H. J. Chem.
Soc., Chem. Commun. 1987, 1093. Canty, A. J.; Watson, A. A. Inorg.
Chim. Acta 1988, 154, 5.
(4) Byers, P. K.; Canty, A. J.; Skelton, B. W.; White, A. H. J. Organomet.
Chem. 1987, 336, C55.
(5) Byers, P. K.; Canty, A. J. J. Chem. Soc., Chem. Commun. 1988,
639.
(6) Recently, several hydrocarbylpalladium(1V) species have been
detected in solution by 'H NMR spectroscopy: (a) Catellani, M.; Chiusoli,
G. P. J. Organomet. Chem. 1988,346, C27. (b) de Graaf, W.; Boersma,
J.; Grove, D.; Spek, A. L.; van Koten, G. Recl. Trau. Chim. Pays-Bas 1988,
107,299. An early report is consistent with detection of a palladium(1V)
intermediate by 'H NMR spectroscopy: (c) Weinberg, E. L.; Hunter, B.
K.; Baird, M. C. J. Organomet. Chem. 1982, 240, 95.
(7) Mono- and bis(pentafluorophenyl)palladium(IV) complexes have
been reported earlier: Uson, R.; Fornies, J.; Navarro, R. Synth. React.
Inorg. Met.-Org. Chem. 1977, 7,235; J. Organomet. Chem. 1975,96,307.
(8) Byers, P. K.; Canty, A. J.; Crespo, M.; Puddephatt, R. J.; Scott, J.
D. Organometallics 1988, 7, 1363.
(9) (a) Dodd, D.; Johnson, M. D.; Lockman, B. L. J. Am. Chem. SOC.
1977, 99, 3664. (b) Stadlbauer, E. A.; Holland, R. J.; Lamm, F. P.;
Schrauzer, G. N. Bioinorg. Chem. 1974, 4, 67. (c) Johnson, R. W.;
Pearson, R. G. J. Chem. Soc., Chem. Commun. 1970,986. (d) Collman,
J. P.; Brauman, J. I.; Madonik, A. M. Organometallics 1986, 5, 215.
(10) Jawad, J. K.; Puddephatt, R. J. Inorg. Chim. Acta 1978,31, L391.
This is one of the classical methods for synthesis of organometallic compounds,
and there are many examples.
(11) (a) Crespo, M.; Puddephatt, R. J. Organometallics 1987,6,2548.
(b) Monaghan, P. K.; Puddephatt, R. J. J. Chem. SOC.D, alton Trans.
1988, 595.
( Mortimer,
C. T.; McNaughton, J. L.; Puddephatt, R. J. J. Chem. SOCD.,a lton Trans.
1972, 1265 and references therein.
.
(14) Benson, S. W. Thermochemical Kinetics, 2nd ed., Wiley: New
York, 1972.
(17) Streitweiser, A. Solvolytic Displacement Reactions; McGraw-Hill:
New York,1 962. Schrauzer, G. N.;D eutsch, E. J. Am. Chem. SOC1.9 69,
91, 3341.
(18) Scott, J. D.; Puddephatt, R. J. Organometallics 1986, 5, 1538.
(19) (a) Ruddick, J. D.; Shaw, B. L. J. Chem. SOCA. 1969,2801. (b)
Brown, M. P.; Puddephatt, R. J.; Upton, C. E. E., J. Chem. SOC.D, alton
Trans. 1974, 2457." name="eprints.referencetext" />
<meta content="Aye, K.-H. and Canty, A.J. and Crespo, M. and Puddephatt, R.J. and Scott, J.D. and Watson, A.A. (1989) Alkyl Halide Transfer from Palladium(IV) to Platinum(II) and a Study of Reactivity, Selectivity, and Mechanism in This and Related Reactions. Organometallics, 8 (6). pp. 1518-1522. ISSN 0276-7333" name="eprints.citation" />
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<meta content="Kinetic studies of the oxidative addition of MeI or PhCH2Br to [MMe2(L2)] (M = Pd or Pt, L2 =
2,2'-bipyridine or 1,lO-phenanthroline) indicate that the reactions occur by the SN2 mechanism, and the reactions occur 7-22 times faster when M = Pt over Pd and 1.2-2.2 times faster when L2 = phen over bpy. Reductive elimination from [PdBrMe2(CH2Ph)(L2)] in the solid state occurs to give both Me-Me and PhCH2Me, and there is a preference for methyl group loss. Thermochemical studies indicate that CH3-CH3 loss gives DH = -108 +/- 4 kJ mol-' but PhCH2-CH3 loss gives DH = -48 +/- 12 kJ mol-', indicating a relatively strong PhCH2-Pd bond. The complexes [PdIMe3(L2)] or [PdBrMe2(CH2Ph)(L2)] react rapidly with [PtMe2(L2)] by alkyl halide transfer. Kinetic studies have shown that the major route involves loss of halide from palladium(IV) in a preequilibrium step, followed by SN2 attack by [PtMe2(L2)] on an alkyl group
of [PdMe3(L2)]+ or [PdMe2(CH2Ph)(L2)]+. In the latter case, benzyl group transfer is preferred over methyl
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<h1 class="ep_tm_pagetitle">Alkyl Halide Transfer from Palladium(IV) to Platinum(II) and a Study of Reactivity, Selectivity, and Mechanism in This and Related Reactions</h1>
<p style="margin-bottom: 1em" class="not_ep_block"><span class="person_name">Aye, K.-H.</span> and <span class="person_name">Canty, A.J.</span> and <span class="person_name">Crespo, M.</span> and <span class="person_name">Puddephatt, R.J.</span> and <span class="person_name">Scott, J.D.</span> and <span class="person_name">Watson, A.A.</span> (1989) <xhtml:em>Alkyl Halide Transfer from Palladium(IV) to Platinum(II) and a Study of Reactivity, Selectivity, and Mechanism in This and Related Reactions.</xhtml:em> Organometallics, 8 (6). pp. 1518-1522. 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/2867/1/Organomet1989_2C_1518.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/2867/1/Organomet1989_2C_1518.pdf"><span class="ep_document_citation">PDF</span></a> - Full text restricted - Requires a PDF viewer<br />653Kb</td><td><form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/request_doc"><input accept-charset="utf-8" value="4093" 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/%20%2010.1021/om00108a024">http://dx.doi.org/ 10.1021/om00108a024</a></p><div class="not_ep_block"><h2>Abstract</h2><p style="padding-bottom: 16px; text-align: left; margin: 1em auto 0em auto">Kinetic studies of the oxidative addition of MeI or PhCH2Br to [MMe2(L2)] (M = Pd or Pt, L2 =
2,2'-bipyridine or 1,lO-phenanthroline) indicate that the reactions occur by the SN2 mechanism, and the reactions occur 7-22 times faster when M = Pt over Pd and 1.2-2.2 times faster when L2 = phen over bpy. Reductive elimination from [PdBrMe2(CH2Ph)(L2)] in the solid state occurs to give both Me-Me and PhCH2Me, and there is a preference for methyl group loss. Thermochemical studies indicate that CH3-CH3 loss gives DH = -108 +/- 4 kJ mol-' but PhCH2-CH3 loss gives DH = -48 +/- 12 kJ mol-', indicating a relatively strong PhCH2-Pd bond. The complexes [PdIMe3(L2)] or [PdBrMe2(CH2Ph)(L2)] react rapidly with [PtMe2(L2)] by alkyl halide transfer. Kinetic studies have shown that the major route involves loss of halide from palladium(IV) in a preequilibrium step, followed by SN2 attack by [PtMe2(L2)] on an alkyl group
of [PdMe3(L2)]+ or [PdMe2(CH2Ph)(L2)]+. In the latter case, benzyl group transfer is preferred over methyl
group transfer.</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">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">2867</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 11:55</td></tr><tr><th valign="top" class="ep_row">Last Modified:</th><td valign="top" class="ep_row">15 Jan 2008 11:55</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=2867;">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=2867">item control page</a></p>
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