Photochemical Resolution of a Thermally Inert Cyclometalated Ru(phbpy)(N–N)(Sulfoxide)+ Complex

In this work a photosubstitution strategy is presented that can be used for the isolation of chiral organometallic complexes. A series of five cyclometalated complexes Ru­(phbpy)­(N−N)­(DMSO-κS)]­(PF6) ([1]­PF6-[5]­PF6) were synthesized and characterized, where Hphbpy = 6′-phenyl-2,2′-bipyridyl, and...

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Veröffentlicht in:Journal of the American Chemical Society 2019-01, Vol.141 (1), p.352-362
Hauptverfasser: Lameijer, Lucien N, van de Griend, Corjan, Hopkins, Samantha L, Volbeda, Anne-Geert, Askes, Sven H. C, Siegler, Maxime A, Bonnet, Sylvestre
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container_issue 1
container_start_page 352
container_title Journal of the American Chemical Society
container_volume 141
creator Lameijer, Lucien N
van de Griend, Corjan
Hopkins, Samantha L
Volbeda, Anne-Geert
Askes, Sven H. C
Siegler, Maxime A
Bonnet, Sylvestre
description In this work a photosubstitution strategy is presented that can be used for the isolation of chiral organometallic complexes. A series of five cyclometalated complexes Ru­(phbpy)­(N−N)­(DMSO-κS)]­(PF6) ([1]­PF6-[5]­PF6) were synthesized and characterized, where Hphbpy = 6′-phenyl-2,2′-bipyridyl, and N–N = bpy (2,2′-bipyridine), phen (1,10-phenanthroline), dpq (pyrazino­[2,3-f]­[1,10]­phenanthroline), dppz (dipyrido­[3,2-a:2′,3′-c]­phenazine, or dppn (benzo­[i]­dipyrido­[3,2-a,2′,3′-c]­phenazine), respectively. Due to the asymmetry of the cyclometalated phbpy– ligand, the corresponding [Ru­(phbpy)­(N–N)­(DMSO-κS)]+complexes are chiral. The exceptional thermal inertness of the Ru–S bond made chiral resolution of these complexes by thermal ligand exchange impossible. However, photosubstitution by visible light irradiation in acetonitrile was possible for three of the five complexes ([1]­PF6-[3]­PF6). Further thermal coordination of the chiral sulfoxide (R)-methyl p-tolylsulfoxide to the photoproduct [Ru­(phbpy)­(phen)­(NCMe)]­PF6, followed by reverse phase HPLC, led to the separation and characterization of the two diastereoisomers of [Ru­(phbpy)­(phen)­(MeSO­(C7H7))]­PF6, thus providing a new photochemical approach toward the synthesis of chiral cyclometalated ruthenium­(II) complexes. Full photochemical, electrochemical, and frontier orbital characterization of the cyclometalated complexes [1]­PF6-[5]­PF6 was performed to explain why [4]­PF6 and [5]­PF6 are photochemically inert while [1]­PF6-[3]­PF6 perform selective photosubstitution.
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The exceptional thermal inertness of the Ru–S bond made chiral resolution of these complexes by thermal ligand exchange impossible. However, photosubstitution by visible light irradiation in acetonitrile was possible for three of the five complexes ([1]­PF6-[3]­PF6). Further thermal coordination of the chiral sulfoxide (R)-methyl p-tolylsulfoxide to the photoproduct [Ru­(phbpy)­(phen)­(NCMe)]­PF6, followed by reverse phase HPLC, led to the separation and characterization of the two diastereoisomers of [Ru­(phbpy)­(phen)­(MeSO­(C7H7))]­PF6, thus providing a new photochemical approach toward the synthesis of chiral cyclometalated ruthenium­(II) complexes. Full photochemical, electrochemical, and frontier orbital characterization of the cyclometalated complexes [1]­PF6-[5]­PF6 was performed to explain why [4]­PF6 and [5]­PF6 are photochemically inert while [1]­PF6-[3]­PF6 perform selective photosubstitution.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.8b10264</identifier><identifier>PMID: 30525567</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 2019-01, Vol.141 (1), p.352-362</ispartof><rights>Copyright © 2018 American Chemical Society 2018 American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a417t-2b544f8ed7bf6ca0608eb51a9818dcc9c0fccb448d5c838d5e99eb10f1234d2d3</citedby><cites>FETCH-LOGICAL-a417t-2b544f8ed7bf6ca0608eb51a9818dcc9c0fccb448d5c838d5e99eb10f1234d2d3</cites><orcidid>0000-0002-5810-3657</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jacs.8b10264$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jacs.8b10264$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/30525567$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Lameijer, Lucien N</creatorcontrib><creatorcontrib>van de Griend, Corjan</creatorcontrib><creatorcontrib>Hopkins, Samantha L</creatorcontrib><creatorcontrib>Volbeda, Anne-Geert</creatorcontrib><creatorcontrib>Askes, Sven H. C</creatorcontrib><creatorcontrib>Siegler, Maxime A</creatorcontrib><creatorcontrib>Bonnet, Sylvestre</creatorcontrib><title>Photochemical Resolution of a Thermally Inert Cyclometalated Ru(phbpy)(N–N)(Sulfoxide)+ Complex</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>In this work a photosubstitution strategy is presented that can be used for the isolation of chiral organometallic complexes. A series of five cyclometalated complexes Ru­(phbpy)­(N−N)­(DMSO-κS)]­(PF6) ([1]­PF6-[5]­PF6) were synthesized and characterized, where Hphbpy = 6′-phenyl-2,2′-bipyridyl, and N–N = bpy (2,2′-bipyridine), phen (1,10-phenanthroline), dpq (pyrazino­[2,3-f]­[1,10]­phenanthroline), dppz (dipyrido­[3,2-a:2′,3′-c]­phenazine, or dppn (benzo­[i]­dipyrido­[3,2-a,2′,3′-c]­phenazine), respectively. Due to the asymmetry of the cyclometalated phbpy– ligand, the corresponding [Ru­(phbpy)­(N–N)­(DMSO-κS)]+complexes are chiral. The exceptional thermal inertness of the Ru–S bond made chiral resolution of these complexes by thermal ligand exchange impossible. However, photosubstitution by visible light irradiation in acetonitrile was possible for three of the five complexes ([1]­PF6-[3]­PF6). Further thermal coordination of the chiral sulfoxide (R)-methyl p-tolylsulfoxide to the photoproduct [Ru­(phbpy)­(phen)­(NCMe)]­PF6, followed by reverse phase HPLC, led to the separation and characterization of the two diastereoisomers of [Ru­(phbpy)­(phen)­(MeSO­(C7H7))]­PF6, thus providing a new photochemical approach toward the synthesis of chiral cyclometalated ruthenium­(II) complexes. 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Soc</addtitle><date>2019-01-09</date><risdate>2019</risdate><volume>141</volume><issue>1</issue><spage>352</spage><epage>362</epage><pages>352-362</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>In this work a photosubstitution strategy is presented that can be used for the isolation of chiral organometallic complexes. A series of five cyclometalated complexes Ru­(phbpy)­(N−N)­(DMSO-κS)]­(PF6) ([1]­PF6-[5]­PF6) were synthesized and characterized, where Hphbpy = 6′-phenyl-2,2′-bipyridyl, and N–N = bpy (2,2′-bipyridine), phen (1,10-phenanthroline), dpq (pyrazino­[2,3-f]­[1,10]­phenanthroline), dppz (dipyrido­[3,2-a:2′,3′-c]­phenazine, or dppn (benzo­[i]­dipyrido­[3,2-a,2′,3′-c]­phenazine), respectively. Due to the asymmetry of the cyclometalated phbpy– ligand, the corresponding [Ru­(phbpy)­(N–N)­(DMSO-κS)]+complexes are chiral. The exceptional thermal inertness of the Ru–S bond made chiral resolution of these complexes by thermal ligand exchange impossible. However, photosubstitution by visible light irradiation in acetonitrile was possible for three of the five complexes ([1]­PF6-[3]­PF6). Further thermal coordination of the chiral sulfoxide (R)-methyl p-tolylsulfoxide to the photoproduct [Ru­(phbpy)­(phen)­(NCMe)]­PF6, followed by reverse phase HPLC, led to the separation and characterization of the two diastereoisomers of [Ru­(phbpy)­(phen)­(MeSO­(C7H7))]­PF6, thus providing a new photochemical approach toward the synthesis of chiral cyclometalated ruthenium­(II) complexes. Full photochemical, electrochemical, and frontier orbital characterization of the cyclometalated complexes [1]­PF6-[5]­PF6 was performed to explain why [4]­PF6 and [5]­PF6 are photochemically inert while [1]­PF6-[3]­PF6 perform selective photosubstitution.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>30525567</pmid><doi>10.1021/jacs.8b10264</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0002-5810-3657</orcidid><oa>free_for_read</oa></addata></record>
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title Photochemical Resolution of a Thermally Inert Cyclometalated Ru(phbpy)(N–N)(Sulfoxide)+ Complex
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