Mechanistic examination of aerobic Pt oxidation: insertion of molecular oxygen into Pt-H bonds through a radical chain mechanism
DFT calculations were performed in an effort to evaluate the mechanism of O 2 insertion into the Pt-H bond of Tp Me 2 Pt IV Me 2 H catalyzed by AIBN or light. Results are consistent with a radical chain mechanism involving H&z.rad; loss to form a Pt III &z.rad; species followed by addition o...
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Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2016-07, Vol.45 (29), p.1165-11656 |
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container_title | Dalton transactions : an international journal of inorganic chemistry |
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creator | Keith, Jason M Ye, Yixin Wei, Haochuan Buck, Matthew R |
description | DFT calculations were performed in an effort to evaluate the mechanism of O
2
insertion into the Pt-H bond of Tp
Me
2
Pt
IV
Me
2
H catalyzed by AIBN or light. Results are consistent with a radical chain mechanism involving H&z.rad; loss to form a Pt
III
&z.rad; species followed by addition of O
2
to form Pt
III
OO&z.rad;. Subsequent radical propagation involving this Pt
III
OO&z.rad; species and an additional equivalent of the Pt
IV
starting material result in the formation of the observed Pt
IV
OOH and regeneration of the Pt
III
&z.rad;. In addition examination of the reaction between AIBN and the Pt
IV
hydroperoxo product demonstrates that radical initiation reactions involving the product occur with a lower barrier than with the initial starting material supporting the idea of autoacceleration in this reaction. Other possible mechanisms were examined in an effort to understand the limited reactivity reported in the absence of light or radical initiators. TDDFT calculations were performed in an effort to understand the reported parallel photo-induced reaction. These calculations found the reactant to be transparent in the relevant light range. An experimental UV-Vis spectrum was obtained and is in agreement with the calculations.
DFT calculations were performed in an effort to evaluate the mechanism of O
2
insertion into the Pt-H bond of Tp
Me
2
Pt
IV
Me
2
H catalyzed by AIBN or light. |
doi_str_mv | 10.1039/c6dt00419a |
format | Article |
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2
insertion into the Pt-H bond of Tp
Me
2
Pt
IV
Me
2
H catalyzed by AIBN or light. Results are consistent with a radical chain mechanism involving H&z.rad; loss to form a Pt
III
&z.rad; species followed by addition of O
2
to form Pt
III
OO&z.rad;. Subsequent radical propagation involving this Pt
III
OO&z.rad; species and an additional equivalent of the Pt
IV
starting material result in the formation of the observed Pt
IV
OOH and regeneration of the Pt
III
&z.rad;. In addition examination of the reaction between AIBN and the Pt
IV
hydroperoxo product demonstrates that radical initiation reactions involving the product occur with a lower barrier than with the initial starting material supporting the idea of autoacceleration in this reaction. Other possible mechanisms were examined in an effort to understand the limited reactivity reported in the absence of light or radical initiators. TDDFT calculations were performed in an effort to understand the reported parallel photo-induced reaction. These calculations found the reactant to be transparent in the relevant light range. An experimental UV-Vis spectrum was obtained and is in agreement with the calculations.
DFT calculations were performed in an effort to evaluate the mechanism of O
2
insertion into the Pt-H bond of Tp
Me
2
Pt
IV
Me
2
H catalyzed by AIBN or light.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c6dt00419a</identifier><identifier>PMID: 27364984</identifier><language>eng</language><publisher>England</publisher><subject>Chains ; Chemical bonds ; Equivalence ; Initiators ; Insertion ; Mathematical analysis ; Platinum ; Radicals</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2016-07, Vol.45 (29), p.1165-11656</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c342t-b9c95934c73946aff7d014ecaf80360ec8495dbee5979e473c8b023f52af1f123</citedby><cites>FETCH-LOGICAL-c342t-b9c95934c73946aff7d014ecaf80360ec8495dbee5979e473c8b023f52af1f123</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/27364984$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Keith, Jason M</creatorcontrib><creatorcontrib>Ye, Yixin</creatorcontrib><creatorcontrib>Wei, Haochuan</creatorcontrib><creatorcontrib>Buck, Matthew R</creatorcontrib><title>Mechanistic examination of aerobic Pt oxidation: insertion of molecular oxygen into Pt-H bonds through a radical chain mechanism</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>DFT calculations were performed in an effort to evaluate the mechanism of O
2
insertion into the Pt-H bond of Tp
Me
2
Pt
IV
Me
2
H catalyzed by AIBN or light. Results are consistent with a radical chain mechanism involving H&z.rad; loss to form a Pt
III
&z.rad; species followed by addition of O
2
to form Pt
III
OO&z.rad;. Subsequent radical propagation involving this Pt
III
OO&z.rad; species and an additional equivalent of the Pt
IV
starting material result in the formation of the observed Pt
IV
OOH and regeneration of the Pt
III
&z.rad;. In addition examination of the reaction between AIBN and the Pt
IV
hydroperoxo product demonstrates that radical initiation reactions involving the product occur with a lower barrier than with the initial starting material supporting the idea of autoacceleration in this reaction. Other possible mechanisms were examined in an effort to understand the limited reactivity reported in the absence of light or radical initiators. TDDFT calculations were performed in an effort to understand the reported parallel photo-induced reaction. These calculations found the reactant to be transparent in the relevant light range. An experimental UV-Vis spectrum was obtained and is in agreement with the calculations.
DFT calculations were performed in an effort to evaluate the mechanism of O
2
insertion into the Pt-H bond of Tp
Me
2
Pt
IV
Me
2
H catalyzed by AIBN or light.</description><subject>Chains</subject><subject>Chemical bonds</subject><subject>Equivalence</subject><subject>Initiators</subject><subject>Insertion</subject><subject>Mathematical analysis</subject><subject>Platinum</subject><subject>Radicals</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqN0TtPwzAQB3ALgWgpLOwgjwgp4FceZkPlKRXBAHPkOGdqlMTFTiTY-OiYtpSVydbdz3eS_wgdUnJGCZfnOqt7QgSVaguNqcjzRDIutjd3lo3QXghvhDBGUraLRiznmZCFGKOvB9Bz1dnQW43hQ7W2U711HXYGK_CuiuWnHrsPWy_rF9h2AfwvaV0DemiUj-LzFbrY7V18kNzhynV1wP3cu-F1jhX2qrZaNTiusx1u12vbfbRjVBPgYH1O0MvN9fP0Lpk93t5PL2eJ5oL1SSW1TCUXOudSZMqYvCZUgFamIDwjoAsh07oCSGUuQeRcFxVh3KRMGWoo4xN0spq78O59gNCXrQ0amkZ14IZQ0oKnGWdS8H9QkpG8iJ8c6emKau9C8GDKhbet8p8lJeVPOOU0u3pehnMZ8fF67lC1UG_obxoRHK2AD3rT_UuXfwNFN5UV</recordid><startdate>20160719</startdate><enddate>20160719</enddate><creator>Keith, Jason M</creator><creator>Ye, Yixin</creator><creator>Wei, Haochuan</creator><creator>Buck, Matthew R</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20160719</creationdate><title>Mechanistic examination of aerobic Pt oxidation: insertion of molecular oxygen into Pt-H bonds through a radical chain mechanism</title><author>Keith, Jason M ; Ye, Yixin ; Wei, Haochuan ; Buck, Matthew R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c342t-b9c95934c73946aff7d014ecaf80360ec8495dbee5979e473c8b023f52af1f123</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Chains</topic><topic>Chemical bonds</topic><topic>Equivalence</topic><topic>Initiators</topic><topic>Insertion</topic><topic>Mathematical analysis</topic><topic>Platinum</topic><topic>Radicals</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Keith, Jason M</creatorcontrib><creatorcontrib>Ye, Yixin</creatorcontrib><creatorcontrib>Wei, Haochuan</creatorcontrib><creatorcontrib>Buck, Matthew R</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Keith, Jason M</au><au>Ye, Yixin</au><au>Wei, Haochuan</au><au>Buck, Matthew R</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanistic examination of aerobic Pt oxidation: insertion of molecular oxygen into Pt-H bonds through a radical chain mechanism</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2016-07-19</date><risdate>2016</risdate><volume>45</volume><issue>29</issue><spage>1165</spage><epage>11656</epage><pages>1165-11656</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>DFT calculations were performed in an effort to evaluate the mechanism of O
2
insertion into the Pt-H bond of Tp
Me
2
Pt
IV
Me
2
H catalyzed by AIBN or light. Results are consistent with a radical chain mechanism involving H&z.rad; loss to form a Pt
III
&z.rad; species followed by addition of O
2
to form Pt
III
OO&z.rad;. Subsequent radical propagation involving this Pt
III
OO&z.rad; species and an additional equivalent of the Pt
IV
starting material result in the formation of the observed Pt
IV
OOH and regeneration of the Pt
III
&z.rad;. In addition examination of the reaction between AIBN and the Pt
IV
hydroperoxo product demonstrates that radical initiation reactions involving the product occur with a lower barrier than with the initial starting material supporting the idea of autoacceleration in this reaction. Other possible mechanisms were examined in an effort to understand the limited reactivity reported in the absence of light or radical initiators. TDDFT calculations were performed in an effort to understand the reported parallel photo-induced reaction. These calculations found the reactant to be transparent in the relevant light range. An experimental UV-Vis spectrum was obtained and is in agreement with the calculations.
DFT calculations were performed in an effort to evaluate the mechanism of O
2
insertion into the Pt-H bond of Tp
Me
2
Pt
IV
Me
2
H catalyzed by AIBN or light.</abstract><cop>England</cop><pmid>27364984</pmid><doi>10.1039/c6dt00419a</doi><tpages>7</tpages></addata></record> |
fulltext | fulltext |
identifier | ISSN: 1477-9226 |
ispartof | Dalton transactions : an international journal of inorganic chemistry, 2016-07, Vol.45 (29), p.1165-11656 |
issn | 1477-9226 1477-9234 |
language | eng |
recordid | cdi_rsc_primary_c6dt00419a |
source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
subjects | Chains Chemical bonds Equivalence Initiators Insertion Mathematical analysis Platinum Radicals |
title | Mechanistic examination of aerobic Pt oxidation: insertion of molecular oxygen into Pt-H bonds through a radical chain mechanism |
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