Influence of nitro substituents on the redox, electronic, and proton reduction catalytic behavior of phenolate-based [NO]-type cobalt() complexes
We report on the synthesis, redox, electronic, and catalytic behavior of two new cobalt( iii ) complexes, namely [Co III (L 1 )MeOH] ( 1 ) and [Co III (L 2 )MeOH] ( 2 ). These species contain nitro-rich, phenolate-based pentadentate ligands and present dramatically distinct properties associated wit...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2019-10, Vol.48 (39), p.14669-14677 |
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| container_issue | 39 |
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| container_title | Dalton transactions : an international journal of inorganic chemistry |
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| creator | Basu, Debashis Mazumder, Shivnath Kpogo, Kenneth K Verani, Cláudio N |
| description | We report on the synthesis, redox, electronic, and catalytic behavior of two new cobalt(
iii
) complexes, namely [Co
III
(L
1
)MeOH] (
1
) and [Co
III
(L
2
)MeOH] (
2
). These species contain nitro-rich, phenolate-based pentadentate ligands and present dramatically distinct properties associated with the position in which the -NO
2
substituents are installed. Species
1
displays nitro-substituted phenolates, and exhibits irreversible redox response and negligible catalytic activity, whereas
2
has fuctionalized phenylene moieties, shows much improved redox reversibility and catalytic proton reduction activity at low overpotentials. A concerted experimental and theoretical approach sheds some light on these drastic differences.
The electronic and redox properties of two new nitro-substituted cobalt species are investigated towards proton reduction. |
| doi_str_mv | 10.1039/c9dt03158h |
| format | Article |
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iii
) complexes, namely [Co
III
(L
1
)MeOH] (
1
) and [Co
III
(L
2
)MeOH] (
2
). These species contain nitro-rich, phenolate-based pentadentate ligands and present dramatically distinct properties associated with the position in which the -NO
2
substituents are installed. Species
1
displays nitro-substituted phenolates, and exhibits irreversible redox response and negligible catalytic activity, whereas
2
has fuctionalized phenylene moieties, shows much improved redox reversibility and catalytic proton reduction activity at low overpotentials. A concerted experimental and theoretical approach sheds some light on these drastic differences.
The electronic and redox properties of two new nitro-substituted cobalt species are investigated towards proton reduction.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c9dt03158h</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Catalytic activity ; Chemical synthesis ; Cobalt ; Crystallography ; Nitrogen dioxide ; NMR ; Nuclear magnetic resonance ; Parameters ; Protons ; Reduction ; Spectra</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2019-10, Vol.48 (39), p.14669-14677</ispartof><rights>Copyright Royal Society of Chemistry 2019</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c308t-3df355c7410b2c294a71791b6ae1048f7ae5bd29e424f7ca0333db2c6b7f4b2e3</citedby><cites>FETCH-LOGICAL-c308t-3df355c7410b2c294a71791b6ae1048f7ae5bd29e424f7ca0333db2c6b7f4b2e3</cites><orcidid>0000-0001-6482-1738 ; 0000-0001-5117-2775 ; 0000000151172775 ; 0000000164821738</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,777,781,882,27905,27906</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/1562736$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Basu, Debashis</creatorcontrib><creatorcontrib>Mazumder, Shivnath</creatorcontrib><creatorcontrib>Kpogo, Kenneth K</creatorcontrib><creatorcontrib>Verani, Cláudio N</creatorcontrib><title>Influence of nitro substituents on the redox, electronic, and proton reduction catalytic behavior of phenolate-based [NO]-type cobalt() complexes</title><title>Dalton transactions : an international journal of inorganic chemistry</title><description>We report on the synthesis, redox, electronic, and catalytic behavior of two new cobalt(
iii
) complexes, namely [Co
III
(L
1
)MeOH] (
1
) and [Co
III
(L
2
)MeOH] (
2
). These species contain nitro-rich, phenolate-based pentadentate ligands and present dramatically distinct properties associated with the position in which the -NO
2
substituents are installed. Species
1
displays nitro-substituted phenolates, and exhibits irreversible redox response and negligible catalytic activity, whereas
2
has fuctionalized phenylene moieties, shows much improved redox reversibility and catalytic proton reduction activity at low overpotentials. A concerted experimental and theoretical approach sheds some light on these drastic differences.
The electronic and redox properties of two new nitro-substituted cobalt species are investigated towards proton reduction.</description><subject>Catalytic activity</subject><subject>Chemical synthesis</subject><subject>Cobalt</subject><subject>Crystallography</subject><subject>Nitrogen dioxide</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Parameters</subject><subject>Protons</subject><subject>Reduction</subject><subject>Spectra</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNpF0ctq3DAUBmATUuhkmk33AdFskhCnutkaL8PkCkNnM12VYqTjY-zgSI4kh8xj5I2r6ZR0pR_p46Cfk2VfGb1iVFTfoWoiFaxYdAfZjEml8ooLefiRefk5OwrhiVLOacFn2fujbYcJLSBxLbF99I6EyYTYx3QbA3GWxA6Jx8a9XRIcEBKxPVwSbRsyeheTSK8TxD4l0FEP29gDMdjp19753dyxQ-sGHTE3OmBDfv1Y_87jdkQCzughnp2n8DwO-IbhS_ap1UPA43_nPPt5d7tZPuSr9f3j8nqVg6CLmIumFUUBSjJqOPBKasVUxUypkVG5aJXGwjS8Qsllq0BTIUSTZGlUKw1HMc--7ee6VLYO0EeEDpy1qWHNipIrUSZ0ukep6MuEIdZPbvI2_avmgjJZCklpUhd7Bd6F4LGtR98_a7-tGa13e6mX1c3m714eEj7ZYx_gw_3fm_gDEzeL9Q</recordid><startdate>20191007</startdate><enddate>20191007</enddate><creator>Basu, Debashis</creator><creator>Mazumder, Shivnath</creator><creator>Kpogo, Kenneth K</creator><creator>Verani, Cláudio N</creator><general>Royal Society of Chemistry</general><general>Royal Society of Chemistry (RSC)</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0001-6482-1738</orcidid><orcidid>https://orcid.org/0000-0001-5117-2775</orcidid><orcidid>https://orcid.org/0000000151172775</orcidid><orcidid>https://orcid.org/0000000164821738</orcidid></search><sort><creationdate>20191007</creationdate><title>Influence of nitro substituents on the redox, electronic, and proton reduction catalytic behavior of phenolate-based [NO]-type cobalt() complexes</title><author>Basu, Debashis ; Mazumder, Shivnath ; Kpogo, Kenneth K ; Verani, Cláudio N</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c308t-3df355c7410b2c294a71791b6ae1048f7ae5bd29e424f7ca0333db2c6b7f4b2e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Catalytic activity</topic><topic>Chemical synthesis</topic><topic>Cobalt</topic><topic>Crystallography</topic><topic>Nitrogen dioxide</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Parameters</topic><topic>Protons</topic><topic>Reduction</topic><topic>Spectra</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Basu, Debashis</creatorcontrib><creatorcontrib>Mazumder, Shivnath</creatorcontrib><creatorcontrib>Kpogo, Kenneth K</creatorcontrib><creatorcontrib>Verani, Cláudio N</creatorcontrib><collection>CrossRef</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><collection>OSTI.GOV</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Basu, Debashis</au><au>Mazumder, Shivnath</au><au>Kpogo, Kenneth K</au><au>Verani, Cláudio N</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Influence of nitro substituents on the redox, electronic, and proton reduction catalytic behavior of phenolate-based [NO]-type cobalt() complexes</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><date>2019-10-07</date><risdate>2019</risdate><volume>48</volume><issue>39</issue><spage>14669</spage><epage>14677</epage><pages>14669-14677</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>We report on the synthesis, redox, electronic, and catalytic behavior of two new cobalt(
iii
) complexes, namely [Co
III
(L
1
)MeOH] (
1
) and [Co
III
(L
2
)MeOH] (
2
). These species contain nitro-rich, phenolate-based pentadentate ligands and present dramatically distinct properties associated with the position in which the -NO
2
substituents are installed. Species
1
displays nitro-substituted phenolates, and exhibits irreversible redox response and negligible catalytic activity, whereas
2
has fuctionalized phenylene moieties, shows much improved redox reversibility and catalytic proton reduction activity at low overpotentials. A concerted experimental and theoretical approach sheds some light on these drastic differences.
The electronic and redox properties of two new nitro-substituted cobalt species are investigated towards proton reduction.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/c9dt03158h</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0001-6482-1738</orcidid><orcidid>https://orcid.org/0000-0001-5117-2775</orcidid><orcidid>https://orcid.org/0000000151172775</orcidid><orcidid>https://orcid.org/0000000164821738</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2019-10, Vol.48 (39), p.14669-14677 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_crossref_primary_10_1039_C9DT03158H |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Catalytic activity Chemical synthesis Cobalt Crystallography Nitrogen dioxide NMR Nuclear magnetic resonance Parameters Protons Reduction Spectra |
| title | Influence of nitro substituents on the redox, electronic, and proton reduction catalytic behavior of phenolate-based [NO]-type cobalt() complexes |
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