Platinum(IV)-Mediated Nitrile−Sulfimide Coupling: A Route to Heterodiazadienes
Pt(IV)-mediated addition of the sulfimide Ph2SNH and the mixed sulfide/sulfimides o- and p-{PhS(NH)}(PhS)C6H4 by the SNH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadie...
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creator | Makarycheva-Mikhailova, Anastassiya V Bokach, Nadezhda A Kukushkin, Vadim Yu Kelly, Paul F Gilby, Liam M Kuznetsov, Maxim L Holmes, Kathryn E Haukka, Matti Parr, Jonathan Stonehouse, Julia M Elsegood, Mark R. J Pombeiro, Armando J. L |
description | Pt(IV)-mediated addition of the sulfimide Ph2SNH and the mixed sulfide/sulfimides o- and p-{PhS(NH)}(PhS)C6H4 by the SNH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4{NHC(R)NSR‘Ph}2] (R‘ = Ph, R = Me, Et, CH2Ph, Ph; R‘ = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2SNH leads exclusively to trans-[PtCl4{NHC(R)NSPh2}2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4{NHC(Me)NSPh2}2] and the latter have been separated by column chromatography. Theoretical calculations at both HF//HF and MP2//HF levels for the cis and trans isomers of [PtCl4{NHC(Me)NSMe2}2] indicate a higher stability for the latter. Compounds trans-[PtCl4{E-NHC(R)NSPh2}2] (R = Me, Et) and cis-[PtCl4{E-NHC(Me)NSPh2}{Z-NHC(Me)NSPh2}] have been characterized by X-ray crystallography. The complexes [PtCl4{NHC(R)NSPh2}2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4{NHC(NH2)R}2] (the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4{NHC(R)NSR‘Ph}2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NHC(R)SR‘Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-{PhS(NH)}(PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the couplingin contrast to the Pt(IV) speciesgives the chelates [PtCl2{NHC(Me)NS(Ph)C6H4SPh}]. The X-ray crystal structure of [PtCl2{NHC(Me)NS(Ph)C6H4SPh-o}] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum. |
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J ; Pombeiro, Armando J. L</creator><creatorcontrib>Makarycheva-Mikhailova, Anastassiya V ; Bokach, Nadezhda A ; Kukushkin, Vadim Yu ; Kelly, Paul F ; Gilby, Liam M ; Kuznetsov, Maxim L ; Holmes, Kathryn E ; Haukka, Matti ; Parr, Jonathan ; Stonehouse, Julia M ; Elsegood, Mark R. J ; Pombeiro, Armando J. L</creatorcontrib><description>Pt(IV)-mediated addition of the sulfimide Ph2SNH and the mixed sulfide/sulfimides o- and p-{PhS(NH)}(PhS)C6H4 by the SNH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4{NHC(R)NSR‘Ph}2] (R‘ = Ph, R = Me, Et, CH2Ph, Ph; R‘ = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2SNH leads exclusively to trans-[PtCl4{NHC(R)NSPh2}2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4{NHC(Me)NSPh2}2] and the latter have been separated by column chromatography. Theoretical calculations at both HF//HF and MP2//HF levels for the cis and trans isomers of [PtCl4{NHC(Me)NSMe2}2] indicate a higher stability for the latter. Compounds trans-[PtCl4{E-NHC(R)NSPh2}2] (R = Me, Et) and cis-[PtCl4{E-NHC(Me)NSPh2}{Z-NHC(Me)NSPh2}] have been characterized by X-ray crystallography. The complexes [PtCl4{NHC(R)NSPh2}2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4{NHC(NH2)R}2] (the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4{NHC(R)NSR‘Ph}2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NHC(R)SR‘Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-{PhS(NH)}(PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the couplingin contrast to the Pt(IV) speciesgives the chelates [PtCl2{NHC(Me)NS(Ph)C6H4SPh}]. The X-ray crystal structure of [PtCl2{NHC(Me)NS(Ph)C6H4SPh-o}] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum.</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/ic025960w</identifier><identifier>PMID: 12693210</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Inorganic chemistry, 2003-01, Vol.42 (2), p.301-311</ispartof><rights>Copyright © 2003 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a349t-5b457a31663f8bd7b7b387bc0cae4904ba874c2345b595d809ec2daa883bddd53</citedby><cites>FETCH-LOGICAL-a349t-5b457a31663f8bd7b7b387bc0cae4904ba874c2345b595d809ec2daa883bddd53</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ic025960w$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ic025960w$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/12693210$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Makarycheva-Mikhailova, Anastassiya V</creatorcontrib><creatorcontrib>Bokach, Nadezhda A</creatorcontrib><creatorcontrib>Kukushkin, Vadim Yu</creatorcontrib><creatorcontrib>Kelly, Paul F</creatorcontrib><creatorcontrib>Gilby, Liam M</creatorcontrib><creatorcontrib>Kuznetsov, Maxim L</creatorcontrib><creatorcontrib>Holmes, Kathryn E</creatorcontrib><creatorcontrib>Haukka, Matti</creatorcontrib><creatorcontrib>Parr, Jonathan</creatorcontrib><creatorcontrib>Stonehouse, Julia M</creatorcontrib><creatorcontrib>Elsegood, Mark R. J</creatorcontrib><creatorcontrib>Pombeiro, Armando J. L</creatorcontrib><title>Platinum(IV)-Mediated Nitrile−Sulfimide Coupling: A Route to Heterodiazadienes</title><title>Inorganic chemistry</title><addtitle>Inorg. Chem</addtitle><description>Pt(IV)-mediated addition of the sulfimide Ph2SNH and the mixed sulfide/sulfimides o- and p-{PhS(NH)}(PhS)C6H4 by the SNH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4{NHC(R)NSR‘Ph}2] (R‘ = Ph, R = Me, Et, CH2Ph, Ph; R‘ = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2SNH leads exclusively to trans-[PtCl4{NHC(R)NSPh2}2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4{NHC(Me)NSPh2}2] and the latter have been separated by column chromatography. Theoretical calculations at both HF//HF and MP2//HF levels for the cis and trans isomers of [PtCl4{NHC(Me)NSMe2}2] indicate a higher stability for the latter. Compounds trans-[PtCl4{E-NHC(R)NSPh2}2] (R = Me, Et) and cis-[PtCl4{E-NHC(Me)NSPh2}{Z-NHC(Me)NSPh2}] have been characterized by X-ray crystallography. The complexes [PtCl4{NHC(R)NSPh2}2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4{NHC(NH2)R}2] (the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4{NHC(R)NSR‘Ph}2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NHC(R)SR‘Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-{PhS(NH)}(PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the couplingin contrast to the Pt(IV) speciesgives the chelates [PtCl2{NHC(Me)NS(Ph)C6H4SPh}]. The X-ray crystal structure of [PtCl2{NHC(Me)NS(Ph)C6H4SPh-o}] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum.</description><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2003</creationdate><recordtype>article</recordtype><recordid>eNptkM9uEzEQhy1ERULgwAtUewGRw4K9ttfr3kIEbVCgVVMqbpa9nlRu90-wvWrpqcf2yiPmSbooUXrpaUaab34z-hB6R_AngjPy2ZU44zLH1y_QkPAMp5zg3y_REOO-J3kuB-h1CJcYY0lZ_goNSJZLmhE8RIuTSkfXdPXH2fk4_QHW6Qg2-emidxWs7_8tumrpamchmbbdqnLNxcH67iGZJKdtFyGJbXIEEXzbL95q66CB8AbtLXUV4O22jtCvb1_Ppkfp_PhwNp3MU02ZjCk3jAtN-__osjBWGGFoIUyJSw1MYmZ0IViZUcYNl9wWWEKZWa2LghprLacj9GGTu_Ltnw5CVLULJVSVbqDtghKUSEEy2oPjDVj6NgQPS7Xyrtb-ryJY_TeodgZ7dn8b2pka7BO5VdYD6QZwIcLNbq79lcoFFVydnSwUywX7Lr4U6rzn3294XQZ12Xa-6Z08c_gRgXOIEw</recordid><startdate>20030127</startdate><enddate>20030127</enddate><creator>Makarycheva-Mikhailova, Anastassiya V</creator><creator>Bokach, Nadezhda A</creator><creator>Kukushkin, Vadim Yu</creator><creator>Kelly, Paul F</creator><creator>Gilby, Liam M</creator><creator>Kuznetsov, Maxim L</creator><creator>Holmes, Kathryn E</creator><creator>Haukka, Matti</creator><creator>Parr, Jonathan</creator><creator>Stonehouse, Julia M</creator><creator>Elsegood, Mark R. J</creator><creator>Pombeiro, Armando J. L</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20030127</creationdate><title>Platinum(IV)-Mediated Nitrile−Sulfimide Coupling: A Route to Heterodiazadienes</title><author>Makarycheva-Mikhailova, Anastassiya V ; Bokach, Nadezhda A ; Kukushkin, Vadim Yu ; Kelly, Paul F ; Gilby, Liam M ; Kuznetsov, Maxim L ; Holmes, Kathryn E ; Haukka, Matti ; Parr, Jonathan ; Stonehouse, Julia M ; Elsegood, Mark R. J ; Pombeiro, Armando J. L</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a349t-5b457a31663f8bd7b7b387bc0cae4904ba874c2345b595d809ec2daa883bddd53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2003</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Makarycheva-Mikhailova, Anastassiya V</creatorcontrib><creatorcontrib>Bokach, Nadezhda A</creatorcontrib><creatorcontrib>Kukushkin, Vadim Yu</creatorcontrib><creatorcontrib>Kelly, Paul F</creatorcontrib><creatorcontrib>Gilby, Liam M</creatorcontrib><creatorcontrib>Kuznetsov, Maxim L</creatorcontrib><creatorcontrib>Holmes, Kathryn E</creatorcontrib><creatorcontrib>Haukka, Matti</creatorcontrib><creatorcontrib>Parr, Jonathan</creatorcontrib><creatorcontrib>Stonehouse, Julia M</creatorcontrib><creatorcontrib>Elsegood, Mark R. J</creatorcontrib><creatorcontrib>Pombeiro, Armando J. L</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Makarycheva-Mikhailova, Anastassiya V</au><au>Bokach, Nadezhda A</au><au>Kukushkin, Vadim Yu</au><au>Kelly, Paul F</au><au>Gilby, Liam M</au><au>Kuznetsov, Maxim L</au><au>Holmes, Kathryn E</au><au>Haukka, Matti</au><au>Parr, Jonathan</au><au>Stonehouse, Julia M</au><au>Elsegood, Mark R. J</au><au>Pombeiro, Armando J. L</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Platinum(IV)-Mediated Nitrile−Sulfimide Coupling: A Route to Heterodiazadienes</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2003-01-27</date><risdate>2003</risdate><volume>42</volume><issue>2</issue><spage>301</spage><epage>311</epage><pages>301-311</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>Pt(IV)-mediated addition of the sulfimide Ph2SNH and the mixed sulfide/sulfimides o- and p-{PhS(NH)}(PhS)C6H4 by the SNH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4{NHC(R)NSR‘Ph}2] (R‘ = Ph, R = Me, Et, CH2Ph, Ph; R‘ = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2SNH leads exclusively to trans-[PtCl4{NHC(R)NSPh2}2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4{NHC(Me)NSPh2}2] and the latter have been separated by column chromatography. Theoretical calculations at both HF//HF and MP2//HF levels for the cis and trans isomers of [PtCl4{NHC(Me)NSMe2}2] indicate a higher stability for the latter. Compounds trans-[PtCl4{E-NHC(R)NSPh2}2] (R = Me, Et) and cis-[PtCl4{E-NHC(Me)NSPh2}{Z-NHC(Me)NSPh2}] have been characterized by X-ray crystallography. The complexes [PtCl4{NHC(R)NSPh2}2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4{NHC(NH2)R}2] (the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4{NHC(R)NSR‘Ph}2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NHC(R)SR‘Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-{PhS(NH)}(PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the couplingin contrast to the Pt(IV) speciesgives the chelates [PtCl2{NHC(Me)NS(Ph)C6H4SPh}]. The X-ray crystal structure of [PtCl2{NHC(Me)NS(Ph)C6H4SPh-o}] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>12693210</pmid><doi>10.1021/ic025960w</doi><tpages>11</tpages></addata></record> |
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