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<meta content="Markies, B.A." name="eprints.creators_name" />
<meta content="Canty, A.J." name="eprints.creators_name" />
<meta content="Boersma, J." name="eprints.creators_name" />
<meta content="van Koten, G." name="eprints.creators_name" />
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<meta content="allan.canty@utas.edu.au" name="eprints.creators_id" />
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<meta content="2007-10-11 00:26:33" name="eprints.datestamp" />
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<meta content="Phenylpalladium(IV) Chemistry: Selectivity in Reductive
Elimination from Palladium(IV) Complexes and Alkyl
Halide Transfer from Palladium(IV) to Palladium(II)" name="eprints.title" />
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<meta content="Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-
bipyridyl) in acetone at 0 °C to form the isolable fuc-triorganopalladium(1V) complexes PdIMez-
Ph(bpy) (3) and PdXMePh(CHzPh)(bpy) [X = Br (4), I (5)l. Complex 3 occurs as a mixture
of isomers in a cu. 1:l ratio, involving the phenyl group in a position trans either to bpy (3a)
or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has
the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal
bonded to three different groups could be studied for the first time. The complexes undergo
facile reductive elimination in (CD3)zCO at 0 °C, in which PdIMezPh(bpy) gives a mixture of
ethane and toluene in a 4:l molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh-
(CHzPh)(bpy) (X = Br, I) gives exclusively toluene and PdX(CHZPh)(bpy). The analogous
tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts
more slowly than PdMePh(bpy1 with alkyl halides. Methyl iodide reacts cleanly with PdMePh-
(tmeda) at 0 °C in (CD3)zC0 to form ethane and PdIPh(tmeda), but the expected palladium(1V)
intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda)
below the decomposition temperature of the latter under these conditions (50 °C, (CD&CO),
while benzyl iodide reacts at 40 °C to give a complicated mixture of products of which ethane,
diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified.
Benzyl iodide reacts with PdMez(tmeda) at -30 °C in (CD3)zCO to form PdIMez(CHzPh)-
(tmeda), for which lH NMR spectra showed the benzyl group to be trans to one of the N-donor
atoms. However, PdIMez(CHzPh) (tmeda) is unstable and undergoes facile reductive elimination
to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium-
(IV) to palladium(I1) complexes occurs in (CD3)zCO at low temperatures for several reaction
systems in which the resulting palladium(1V) complex is known to be more stable than the
palladium(1V) reagent. There is a strong preference for benzyl group transfer from PdXMePh-
(CHZPh)(bpy) to PdMez(L2) (X = Br, I; LZ = bpy, phen). The mechanism of the transfer
reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from
palladium(1V) to platinum(II), palladium(I1) to palladium(O), cobalt(II1) to cobalt(I), and
rhodium(II1) to rhodium(1). These reaction systems involve nucleophilic attack by the lower
oxidation state reagent at an alkyl group attached to the higher oxidation state reagent." name="eprints.abstract" />
<meta content="1994-05" name="eprints.date" />
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<meta content="Organometallics" name="eprints.publication" />
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<meta content="5" name="eprints.number" />
<meta content="2053-2058" name="eprints.pagerange" />
<meta content="10.1021/om00017a071" name="eprints.id_number" />
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<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" />
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Elimination from Palladium(IV) Complexes and Alkyl
Halide Transfer from Palladium(IV) to Palladium(II)" name="DC.title" />
<meta content="Markies, B.A." name="DC.creator" />
<meta content="Canty, A.J." name="DC.creator" />
<meta content="Boersma, J." name="DC.creator" />
<meta content="van Koten, G." name="DC.creator" />
<meta content="259901 Organometallic Chemistry" name="DC.subject" />
<meta content="Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-
bipyridyl) in acetone at 0 °C to form the isolable fuc-triorganopalladium(1V) complexes PdIMez-
Ph(bpy) (3) and PdXMePh(CHzPh)(bpy) [X = Br (4), I (5)l. Complex 3 occurs as a mixture
of isomers in a cu. 1:l ratio, involving the phenyl group in a position trans either to bpy (3a)
or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has
the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal
bonded to three different groups could be studied for the first time. The complexes undergo
facile reductive elimination in (CD3)zCO at 0 °C, in which PdIMezPh(bpy) gives a mixture of
ethane and toluene in a 4:l molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh-
(CHzPh)(bpy) (X = Br, I) gives exclusively toluene and PdX(CHZPh)(bpy). The analogous
tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts
more slowly than PdMePh(bpy1 with alkyl halides. Methyl iodide reacts cleanly with PdMePh-
(tmeda) at 0 °C in (CD3)zC0 to form ethane and PdIPh(tmeda), but the expected palladium(1V)
intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda)
below the decomposition temperature of the latter under these conditions (50 °C, (CD&CO),
while benzyl iodide reacts at 40 °C to give a complicated mixture of products of which ethane,
diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified.
Benzyl iodide reacts with PdMez(tmeda) at -30 °C in (CD3)zCO to form PdIMez(CHzPh)-
(tmeda), for which lH NMR spectra showed the benzyl group to be trans to one of the N-donor
atoms. However, PdIMez(CHzPh) (tmeda) is unstable and undergoes facile reductive elimination
to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium-
(IV) to palladium(I1) complexes occurs in (CD3)zCO at low temperatures for several reaction
systems in which the resulting palladium(1V) complex is known to be more stable than the
palladium(1V) reagent. There is a strong preference for benzyl group transfer from PdXMePh-
(CHZPh)(bpy) to PdMez(L2) (X = Br, I; LZ = bpy, phen). The mechanism of the transfer
reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from
palladium(1V) to platinum(II), palladium(I1) to palladium(O), cobalt(II1) to cobalt(I), and
rhodium(II1) to rhodium(1). These reaction systems involve nucleophilic attack by the lower
oxidation state reagent at an alkyl group attached to the higher oxidation state reagent." name="DC.description" />
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<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>
<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'-
bipyridyl) in acetone at 0 °C to form the isolable fuc-triorganopalladium(1V) complexes PdIMez-
Ph(bpy) (3) and PdXMePh(CHzPh)(bpy) [X = Br (4), I (5)l. Complex 3 occurs as a mixture
of isomers in a cu. 1:l ratio, involving the phenyl group in a position trans either to bpy (3a)
or to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has
the benzyl group trans to the halogen. The selectivity of reductive elimination from a metal
bonded to three different groups could be studied for the first time. The complexes undergo
facile reductive elimination in (CD3)zCO at 0 °C, in which PdIMezPh(bpy) gives a mixture of
ethane and toluene in a 4:l molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh-
(CHzPh)(bpy) (X = Br, I) gives exclusively toluene and PdX(CHZPh)(bpy). The analogous
tmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts
more slowly than PdMePh(bpy1 with alkyl halides. Methyl iodide reacts cleanly with PdMePh-
(tmeda) at 0 °C in (CD3)zC0 to form ethane and PdIPh(tmeda), but the expected palladium(1V)
intermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda)
below the decomposition temperature of the latter under these conditions (50 °C, (CD&CO),
while benzyl iodide reacts at 40 °C to give a complicated mixture of products of which ethane,
diphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified.
Benzyl iodide reacts with PdMez(tmeda) at -30 °C in (CD3)zCO to form PdIMez(CHzPh)-
(tmeda), for which lH NMR spectra showed the benzyl group to be trans to one of the N-donor
atoms. However, PdIMez(CHzPh) (tmeda) is unstable and undergoes facile reductive elimination
to form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium-
(IV) to palladium(I1) complexes occurs in (CD3)zCO at low temperatures for several reaction
systems in which the resulting palladium(1V) complex is known to be more stable than the
palladium(1V) reagent. There is a strong preference for benzyl group transfer from PdXMePh-
(CHZPh)(bpy) to PdMez(L2) (X = Br, I; LZ = bpy, phen). The mechanism of the transfer
reactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from
palladium(1V) to platinum(II), palladium(I1) to palladium(O), cobalt(II1) to cobalt(I), and
rhodium(II1) to rhodium(1). These reaction systems involve nucleophilic attack by the lower
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 > 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">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&eprintid=2069">item control page</a></p>
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