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  5.     <title>UTas ePrints - Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II)</title>
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  13.     <meta content="Markies, B.A." name="eprints.creators_name" />
  14. <meta content="Canty, A.J." name="eprints.creators_name" />
  15. <meta content="Boersma, J." name="eprints.creators_name" />
  16. <meta content="van Koten, G." name="eprints.creators_name" />
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  18. <meta content="allan.canty@utas.edu.au" name="eprints.creators_id" />
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  22. <meta content="2007-10-11 00:26:33" name="eprints.datestamp" />
  23. <meta content="2008-02-01T03:57:45Z" name="eprints.lastmod" />
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  25. <meta content="Phenylpalladium(IV) Chemistry: Selectivity in Reductive
  26. Elimination from Palladium(IV) Complexes and Alkyl
  27. Halide Transfer from Palladium(IV) to Palladium(II)" name="eprints.title" />
  28. <meta content="pub" name="eprints.ispublished" />
  29. <meta content="259901" name="eprints.subjects" />
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  31. <meta content="Definitive version is available online at http://pubs.acs.org/journals/orgnd7/index.html" name="eprints.note" />
  32. <meta content="Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-
  33. bipyridyl) in acetone at 0 °C to form the isolable fuc-triorganopalladium(1V) complexes PdIMez-
  34. Ph(bpy) (3) and PdXMePh(CHzPh)(bpy) [X = Br (4), I (5)l. Complex 3 occurs as a mixture
  35. of isomers in a cu. 1:l ratio, involving the phenyl group in a position trans either to bpy (3a)
  36. or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has
  37. the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal
  38. bonded to three different groups could be studied for the first time. The complexes undergo
  39. facile reductive elimination in (CD3)zCO at 0 °C, in which PdIMezPh(bpy) gives a mixture of
  40. ethane and toluene in a 4:l molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh-
  41. (CHzPh)(bpy) (X = Br, I) gives exclusively toluene and PdX(CHZPh)(bpy). The analogous
  42. tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts
  43. more slowly than PdMePh(bpy1 with alkyl halides. Methyl iodide reacts cleanly with PdMePh-
  44. (tmeda) at 0 °C in (CD3)zC0 to form ethane and PdIPh(tmeda), but the expected palladium(1V)
  45. intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda)
  46. below the decomposition temperature of the latter under these conditions (50 °C, (CD&amp;CO),
  47. while benzyl iodide reacts at 40 °C to give a complicated mixture of products of which ethane,
  48. diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified.
  49. Benzyl iodide reacts with PdMez(tmeda) at -30 °C in (CD3)zCO to form PdIMez(CHzPh)-
  50. (tmeda), for which lH NMR spectra showed the benzyl group to be trans to one of the N-donor
  51. atoms. However, PdIMez(CHzPh) (tmeda) is unstable and undergoes facile reductive elimination
  52. to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium-
  53. (IV) to palladium(I1) complexes occurs in (CD3)zCO at low temperatures for several reaction
  54. systems in which the resulting palladium(1V) complex is known to be more stable than the
  55. palladium(1V) reagent. There is a strong preference for benzyl group transfer from PdXMePh-
  56. (CHZPh)(bpy) to PdMez(L2) (X = Br, I; LZ = bpy, phen). The mechanism of the transfer
  57. reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from
  58. palladium(1V) to platinum(II), palladium(I1) to palladium(O), cobalt(II1) to cobalt(I), and
  59. rhodium(II1) to rhodium(1). These reaction systems involve nucleophilic attack by the lower
  60. oxidation state reagent at an alkyl group attached to the higher oxidation state reagent." name="eprints.abstract" />
  61. <meta content="1994-05" name="eprints.date" />
  62. <meta content="published" name="eprints.date_type" />
  63. <meta content="Organometallics" name="eprints.publication" />
  64. <meta content="13" name="eprints.volume" />
  65. <meta content="5" name="eprints.number" />
  66. <meta content="2053-2058" name="eprints.pagerange" />
  67. <meta content="10.1021/om00017a071" name="eprints.id_number" />
  68. <meta content="TRUE" name="eprints.refereed" />
  69. <meta content="0276-7333" name="eprints.issn" />
  70. <meta content="http://dx.doi.org/10.1021/om00017a071" name="eprints.official_url" />
  71. <meta content="Markies, B.A. and Canty, A.J. and Boersma, J. and van Koten, G. (1994) Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II). Organometallics, 13 (5). pp. 2053-2058. ISSN 0276-7333" name="eprints.citation" />
  72. <meta content="http://eprints.utas.edu.au/2069/1/om00017a071.pdf" name="eprints.document_url" />
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  74. <meta content="Phenylpalladium(IV) Chemistry: Selectivity in Reductive
  75. Elimination from Palladium(IV) Complexes and Alkyl
  76. Halide Transfer from Palladium(IV) to Palladium(II)" name="DC.title" />
  77. <meta content="Markies, B.A." name="DC.creator" />
  78. <meta content="Canty, A.J." name="DC.creator" />
  79. <meta content="Boersma, J." name="DC.creator" />
  80. <meta content="van Koten, G." name="DC.creator" />
  81. <meta content="259901 Organometallic Chemistry" name="DC.subject" />
  82. <meta content="Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-
  83. bipyridyl) in acetone at 0 °C to form the isolable fuc-triorganopalladium(1V) complexes PdIMez-
  84. Ph(bpy) (3) and PdXMePh(CHzPh)(bpy) [X = Br (4), I (5)l. Complex 3 occurs as a mixture
  85. of isomers in a cu. 1:l ratio, involving the phenyl group in a position trans either to bpy (3a)
  86. or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has
  87. the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal
  88. bonded to three different groups could be studied for the first time. The complexes undergo
  89. facile reductive elimination in (CD3)zCO at 0 °C, in which PdIMezPh(bpy) gives a mixture of
  90. ethane and toluene in a 4:l molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh-
  91. (CHzPh)(bpy) (X = Br, I) gives exclusively toluene and PdX(CHZPh)(bpy). The analogous
  92. tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts
  93. more slowly than PdMePh(bpy1 with alkyl halides. Methyl iodide reacts cleanly with PdMePh-
  94. (tmeda) at 0 °C in (CD3)zC0 to form ethane and PdIPh(tmeda), but the expected palladium(1V)
  95. intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda)
  96. below the decomposition temperature of the latter under these conditions (50 °C, (CD&amp;CO),
  97. while benzyl iodide reacts at 40 °C to give a complicated mixture of products of which ethane,
  98. diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified.
  99. Benzyl iodide reacts with PdMez(tmeda) at -30 °C in (CD3)zCO to form PdIMez(CHzPh)-
  100. (tmeda), for which lH NMR spectra showed the benzyl group to be trans to one of the N-donor
  101. atoms. However, PdIMez(CHzPh) (tmeda) is unstable and undergoes facile reductive elimination
  102. to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium-
  103. (IV) to palladium(I1) complexes occurs in (CD3)zCO at low temperatures for several reaction
  104. systems in which the resulting palladium(1V) complex is known to be more stable than the
  105. palladium(1V) reagent. There is a strong preference for benzyl group transfer from PdXMePh-
  106. (CHZPh)(bpy) to PdMez(L2) (X = Br, I; LZ = bpy, phen). The mechanism of the transfer
  107. reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from
  108. palladium(1V) to platinum(II), palladium(I1) to palladium(O), cobalt(II1) to cobalt(I), and
  109. rhodium(II1) to rhodium(1). These reaction systems involve nucleophilic attack by the lower
  110. oxidation state reagent at an alkyl group attached to the higher oxidation state reagent." name="DC.description" />
  111. <meta content="1994-05" name="DC.date" />
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  117. <meta content="Markies, B.A. and Canty, A.J. and Boersma, J. and van Koten, G. (1994) Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II). Organometallics, 13 (5). pp. 2053-2058. ISSN 0276-7333" name="DC.identifier" />
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  224.     <h1 class="ep_tm_pagetitle">Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II)</h1>
  225.     <p style="margin-bottom: 1em" class="not_ep_block"><span class="person_name">Markies, B.A.</span> and <span class="person_name">Canty, A.J.</span> and <span class="person_name">Boersma, J.</span> and <span class="person_name">van Koten, G.</span> (1994) <xhtml:em>Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II).</xhtml:em> Organometallics, 13 (5). pp. 2053-2058. 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/2069/1/om00017a071.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/2069/1/om00017a071.pdf"><span class="ep_document_citation">PDF</span></a> - Full text restricted - Requires a PDF viewer<br />773Kb</td><td><form method="get" accept-charset="utf-8" action="http://eprints.utas.edu.au/cgi/request_doc"><input accept-charset="utf-8" value="2608" 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/10.1021/om00017a071">http://dx.doi.org/10.1021/om00017a071</a></p><div class="not_ep_block"><h2>Abstract</h2><p style="padding-bottom: 16px; text-align: left; margin: 1em auto 0em auto">Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-&#13;
  226. bipyridyl) in acetone at 0 °C to form the isolable fuc-triorganopalladium(1V) complexes PdIMez-&#13;
  227. Ph(bpy) (3) and PdXMePh(CHzPh)(bpy) [X = Br (4), I (5)l. Complex 3 occurs as a mixture&#13;
  228. of isomers in a cu. 1:l ratio, involving the phenyl group in a position trans either to bpy (3a)&#13;
  229. or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has&#13;
  230. the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal&#13;
  231. bonded to three different groups could be studied for the first time. The complexes undergo&#13;
  232. facile reductive elimination in (CD3)zCO at 0 °C, in which PdIMezPh(bpy) gives a mixture of&#13;
  233. ethane and toluene in a 4:l molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh-&#13;
  234. (CHzPh)(bpy) (X = Br, I) gives exclusively toluene and PdX(CHZPh)(bpy). The analogous&#13;
  235. tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts&#13;
  236. more slowly than PdMePh(bpy1 with alkyl halides. Methyl iodide reacts cleanly with PdMePh-&#13;
  237. (tmeda) at 0 °C in (CD3)zC0 to form ethane and PdIPh(tmeda), but the expected palladium(1V)&#13;
  238. intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda)&#13;
  239. below the decomposition temperature of the latter under these conditions (50 °C, (CD&amp;CO),&#13;
  240. while benzyl iodide reacts at 40 °C to give a complicated mixture of products of which ethane,&#13;
  241. diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified.&#13;
  242. Benzyl iodide reacts with PdMez(tmeda) at -30 °C in (CD3)zCO to form PdIMez(CHzPh)-&#13;
  243. (tmeda), for which lH NMR spectra showed the benzyl group to be trans to one of the N-donor&#13;
  244. atoms. However, PdIMez(CHzPh) (tmeda) is unstable and undergoes facile reductive elimination&#13;
  245. to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium-&#13;
  246. (IV) to palladium(I1) complexes occurs in (CD3)zCO at low temperatures for several reaction&#13;
  247. systems in which the resulting palladium(1V) complex is known to be more stable than the&#13;
  248. palladium(1V) reagent. There is a strong preference for benzyl group transfer from PdXMePh-&#13;
  249. (CHZPh)(bpy) to PdMez(L2) (X = Br, I; LZ = bpy, phen). The mechanism of the transfer&#13;
  250. reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from&#13;
  251. palladium(1V) to platinum(II), palladium(I1) to palladium(O), cobalt(II1) to cobalt(I), and&#13;
  252. rhodium(II1) to rhodium(1). These reaction systems involve nucleophilic attack by the lower&#13;
  253. oxidation state reagent at an alkyl group attached to the higher oxidation state reagent.</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">Definitive version is available online at http://pubs.acs.org/journals/orgnd7/index.html</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 &gt; 259900 Other Chemical Sciences &gt; 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">2069</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">11 Oct 2007 11:26</td></tr><tr><th valign="top" class="ep_row">Last Modified:</th><td valign="top" class="ep_row">01 Feb 2008 14:57</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=2069;">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&amp;eprintid=2069">item control page</a></p>
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