Catalytic N 2 Reduction to Silylamines and Thermodynamics of N 2 Binding at Square Planar Fe
The geometric constraints imposed by a tetradentate P N ligand play an essential role in stabilizing square planar Fe complexes with changes in metal oxidation state. The square pyramidal Fe (N )(P N ) complex catalyzes the conversion of N to N(SiR ) (R = Me, Et) at room temperature, representing th...
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| Veröffentlicht in: | Journal of the American Chemical Society 2017-07, Vol.139 (27), p.9291-9301 |
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| creator | Prokopchuk, Demyan E Wiedner, Eric S Walter, Eric D Popescu, Codrina V Piro, Nicholas A Kassel, W Scott Bullock, R Morris Mock, Michael T |
| description | The geometric constraints imposed by a tetradentate P
N
ligand play an essential role in stabilizing square planar Fe complexes with changes in metal oxidation state. The square pyramidal Fe
(N
)(P
N
) complex catalyzes the conversion of N
to N(SiR
)
(R = Me, Et) at room temperature, representing the highest turnover number of any Fe-based N
silylation catalyst to date (up to 65 equiv N(SiMe
)
per Fe center). Elevated N
pressures (>1 atm) have a dramatic effect on catalysis, increasing N
solubility and the thermodynamic N
binding affinity at Fe
(N
)(P
N
). A combination of high-pressure electrochemistry and variable-temperature UV-vis spectroscopy were used to obtain thermodynamic measurements of N
binding. In addition, X-ray crystallography,
Fe Mössbauer spectroscopy, and EPR spectroscopy were used to fully characterize these new compounds. Analysis of Fe
, Fe
, and Fe
complexes reveals that the free energy of N
binding across three oxidation states spans more than 37 kcal mol
. |
| doi_str_mv | 10.1021/jacs.7b04552 |
| format | Article |
| fullrecord | <record><control><sourceid>pubmed_osti_</sourceid><recordid>TN_cdi_osti_scitechconnect_1378028</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>28613896</sourcerecordid><originalsourceid>FETCH-LOGICAL-c215t-f39847dbc6c8cbc5d632d4af3a0a96ce0b7d405e2b26b31082b2c8aa800463da3</originalsourceid><addsrcrecordid>eNo9kE1PwzAMhiMEYmNw44wiznTko02zI0wMkCZAbNyQKtdJWaYuHU122L-nY4OT7VePLfkh5JKzIWeC3y4BwzAvWZpl4oj0eSZYknGhjkmfMSaSXCvZI2chLLsxFZqfkp7Qiks9Un3yOYYI9TY6pC9U0HdrNhhd42ls6MzV2xpWzttAwRs6X9h21Zit7zIMtKl-V-6dN85_UYh09r2B1tK3Gjy0dGLPyUkFdbAXhzogH5OH-fgpmb4-Po_vpgkKnsWkkiOd5qZEhRpLzIySwqRQSWAwUmhZmZuUZVaUQpWSM901qAF094-SBuSAXO_vNiG6IqCLFhfYeG8xFlzmmgndQTd7CNsmhNZWxbp1K2i3BWfFzmSxM1kcTHb41R5fb8qVNf_wnzr5A3MubkI</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Catalytic N 2 Reduction to Silylamines and Thermodynamics of N 2 Binding at Square Planar Fe</title><source>American Chemical Society</source><creator>Prokopchuk, Demyan E ; Wiedner, Eric S ; Walter, Eric D ; Popescu, Codrina V ; Piro, Nicholas A ; Kassel, W Scott ; Bullock, R Morris ; Mock, Michael T</creator><creatorcontrib>Prokopchuk, Demyan E ; Wiedner, Eric S ; Walter, Eric D ; Popescu, Codrina V ; Piro, Nicholas A ; Kassel, W Scott ; Bullock, R Morris ; Mock, Michael T ; Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME) ; Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)</creatorcontrib><description>The geometric constraints imposed by a tetradentate P
N
ligand play an essential role in stabilizing square planar Fe complexes with changes in metal oxidation state. The square pyramidal Fe
(N
)(P
N
) complex catalyzes the conversion of N
to N(SiR
)
(R = Me, Et) at room temperature, representing the highest turnover number of any Fe-based N
silylation catalyst to date (up to 65 equiv N(SiMe
)
per Fe center). Elevated N
pressures (>1 atm) have a dramatic effect on catalysis, increasing N
solubility and the thermodynamic N
binding affinity at Fe
(N
)(P
N
). A combination of high-pressure electrochemistry and variable-temperature UV-vis spectroscopy were used to obtain thermodynamic measurements of N
binding. In addition, X-ray crystallography,
Fe Mössbauer spectroscopy, and EPR spectroscopy were used to fully characterize these new compounds. Analysis of Fe
, Fe
, and Fe
complexes reveals that the free energy of N
binding across three oxidation states spans more than 37 kcal mol
.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.7b04552</identifier><identifier>PMID: 28613896</identifier><language>eng</language><publisher>United States: American Chemical Society (ACS)</publisher><subject>dinitrogen ; Environmental Molecular Sciences Laboratory ; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ; iron ; Mossbauer ; square planer ; thermodynamics</subject><ispartof>Journal of the American Chemical Society, 2017-07, Vol.139 (27), p.9291-9301</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c215t-f39847dbc6c8cbc5d632d4af3a0a96ce0b7d405e2b26b31082b2c8aa800463da3</citedby><cites>FETCH-LOGICAL-c215t-f39847dbc6c8cbc5d632d4af3a0a96ce0b7d405e2b26b31082b2c8aa800463da3</cites><orcidid>0000-0003-4219-0909 ; 0000-0002-7202-9676 ; 0000-0002-7310-2791 ; 0000-0001-6306-4851 ; 0000-0002-6764-9045 ; 0000-0002-6352-3509 ; 0000000272029676 ; 0000000267649045 ; 0000000263523509 ; 0000000163064851 ; 0000000273102791 ; 0000000342190909</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,777,781,882,2752,27905,27906</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28613896$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/1378028$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Prokopchuk, Demyan E</creatorcontrib><creatorcontrib>Wiedner, Eric S</creatorcontrib><creatorcontrib>Walter, Eric D</creatorcontrib><creatorcontrib>Popescu, Codrina V</creatorcontrib><creatorcontrib>Piro, Nicholas A</creatorcontrib><creatorcontrib>Kassel, W Scott</creatorcontrib><creatorcontrib>Bullock, R Morris</creatorcontrib><creatorcontrib>Mock, Michael T</creatorcontrib><creatorcontrib>Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)</creatorcontrib><creatorcontrib>Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)</creatorcontrib><title>Catalytic N 2 Reduction to Silylamines and Thermodynamics of N 2 Binding at Square Planar Fe</title><title>Journal of the American Chemical Society</title><addtitle>J Am Chem Soc</addtitle><description>The geometric constraints imposed by a tetradentate P
N
ligand play an essential role in stabilizing square planar Fe complexes with changes in metal oxidation state. The square pyramidal Fe
(N
)(P
N
) complex catalyzes the conversion of N
to N(SiR
)
(R = Me, Et) at room temperature, representing the highest turnover number of any Fe-based N
silylation catalyst to date (up to 65 equiv N(SiMe
)
per Fe center). Elevated N
pressures (>1 atm) have a dramatic effect on catalysis, increasing N
solubility and the thermodynamic N
binding affinity at Fe
(N
)(P
N
). A combination of high-pressure electrochemistry and variable-temperature UV-vis spectroscopy were used to obtain thermodynamic measurements of N
binding. In addition, X-ray crystallography,
Fe Mössbauer spectroscopy, and EPR spectroscopy were used to fully characterize these new compounds. Analysis of Fe
, Fe
, and Fe
complexes reveals that the free energy of N
binding across three oxidation states spans more than 37 kcal mol
.</description><subject>dinitrogen</subject><subject>Environmental Molecular Sciences Laboratory</subject><subject>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</subject><subject>iron</subject><subject>Mossbauer</subject><subject>square planer</subject><subject>thermodynamics</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNo9kE1PwzAMhiMEYmNw44wiznTko02zI0wMkCZAbNyQKtdJWaYuHU122L-nY4OT7VePLfkh5JKzIWeC3y4BwzAvWZpl4oj0eSZYknGhjkmfMSaSXCvZI2chLLsxFZqfkp7Qiks9Un3yOYYI9TY6pC9U0HdrNhhd42ls6MzV2xpWzttAwRs6X9h21Zit7zIMtKl-V-6dN85_UYh09r2B1tK3Gjy0dGLPyUkFdbAXhzogH5OH-fgpmb4-Po_vpgkKnsWkkiOd5qZEhRpLzIySwqRQSWAwUmhZmZuUZVaUQpWSM901qAF094-SBuSAXO_vNiG6IqCLFhfYeG8xFlzmmgndQTd7CNsmhNZWxbp1K2i3BWfFzmSxM1kcTHb41R5fb8qVNf_wnzr5A3MubkI</recordid><startdate>20170712</startdate><enddate>20170712</enddate><creator>Prokopchuk, Demyan E</creator><creator>Wiedner, Eric S</creator><creator>Walter, Eric D</creator><creator>Popescu, Codrina V</creator><creator>Piro, Nicholas A</creator><creator>Kassel, W Scott</creator><creator>Bullock, R Morris</creator><creator>Mock, Michael T</creator><general>American Chemical Society (ACS)</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0003-4219-0909</orcidid><orcidid>https://orcid.org/0000-0002-7202-9676</orcidid><orcidid>https://orcid.org/0000-0002-7310-2791</orcidid><orcidid>https://orcid.org/0000-0001-6306-4851</orcidid><orcidid>https://orcid.org/0000-0002-6764-9045</orcidid><orcidid>https://orcid.org/0000-0002-6352-3509</orcidid><orcidid>https://orcid.org/0000000272029676</orcidid><orcidid>https://orcid.org/0000000267649045</orcidid><orcidid>https://orcid.org/0000000263523509</orcidid><orcidid>https://orcid.org/0000000163064851</orcidid><orcidid>https://orcid.org/0000000273102791</orcidid><orcidid>https://orcid.org/0000000342190909</orcidid></search><sort><creationdate>20170712</creationdate><title>Catalytic N 2 Reduction to Silylamines and Thermodynamics of N 2 Binding at Square Planar Fe</title><author>Prokopchuk, Demyan E ; Wiedner, Eric S ; Walter, Eric D ; Popescu, Codrina V ; Piro, Nicholas A ; Kassel, W Scott ; Bullock, R Morris ; Mock, Michael T</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c215t-f39847dbc6c8cbc5d632d4af3a0a96ce0b7d405e2b26b31082b2c8aa800463da3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>dinitrogen</topic><topic>Environmental Molecular Sciences Laboratory</topic><topic>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</topic><topic>iron</topic><topic>Mossbauer</topic><topic>square planer</topic><topic>thermodynamics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Prokopchuk, Demyan E</creatorcontrib><creatorcontrib>Wiedner, Eric S</creatorcontrib><creatorcontrib>Walter, Eric D</creatorcontrib><creatorcontrib>Popescu, Codrina V</creatorcontrib><creatorcontrib>Piro, Nicholas A</creatorcontrib><creatorcontrib>Kassel, W Scott</creatorcontrib><creatorcontrib>Bullock, R Morris</creatorcontrib><creatorcontrib>Mock, Michael T</creatorcontrib><creatorcontrib>Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)</creatorcontrib><creatorcontrib>Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Prokopchuk, Demyan E</au><au>Wiedner, Eric S</au><au>Walter, Eric D</au><au>Popescu, Codrina V</au><au>Piro, Nicholas A</au><au>Kassel, W Scott</au><au>Bullock, R Morris</au><au>Mock, Michael T</au><aucorp>Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)</aucorp><aucorp>Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Catalytic N 2 Reduction to Silylamines and Thermodynamics of N 2 Binding at Square Planar Fe</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J Am Chem Soc</addtitle><date>2017-07-12</date><risdate>2017</risdate><volume>139</volume><issue>27</issue><spage>9291</spage><epage>9301</epage><pages>9291-9301</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>The geometric constraints imposed by a tetradentate P
N
ligand play an essential role in stabilizing square planar Fe complexes with changes in metal oxidation state. The square pyramidal Fe
(N
)(P
N
) complex catalyzes the conversion of N
to N(SiR
)
(R = Me, Et) at room temperature, representing the highest turnover number of any Fe-based N
silylation catalyst to date (up to 65 equiv N(SiMe
)
per Fe center). Elevated N
pressures (>1 atm) have a dramatic effect on catalysis, increasing N
solubility and the thermodynamic N
binding affinity at Fe
(N
)(P
N
). A combination of high-pressure electrochemistry and variable-temperature UV-vis spectroscopy were used to obtain thermodynamic measurements of N
binding. In addition, X-ray crystallography,
Fe Mössbauer spectroscopy, and EPR spectroscopy were used to fully characterize these new compounds. Analysis of Fe
, Fe
, and Fe
complexes reveals that the free energy of N
binding across three oxidation states spans more than 37 kcal mol
.</abstract><cop>United States</cop><pub>American Chemical Society (ACS)</pub><pmid>28613896</pmid><doi>10.1021/jacs.7b04552</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0003-4219-0909</orcidid><orcidid>https://orcid.org/0000-0002-7202-9676</orcidid><orcidid>https://orcid.org/0000-0002-7310-2791</orcidid><orcidid>https://orcid.org/0000-0001-6306-4851</orcidid><orcidid>https://orcid.org/0000-0002-6764-9045</orcidid><orcidid>https://orcid.org/0000-0002-6352-3509</orcidid><orcidid>https://orcid.org/0000000272029676</orcidid><orcidid>https://orcid.org/0000000267649045</orcidid><orcidid>https://orcid.org/0000000263523509</orcidid><orcidid>https://orcid.org/0000000163064851</orcidid><orcidid>https://orcid.org/0000000273102791</orcidid><orcidid>https://orcid.org/0000000342190909</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0002-7863 |
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| issn | 0002-7863 1520-5126 |
| language | eng |
| recordid | cdi_osti_scitechconnect_1378028 |
| source | American Chemical Society |
| subjects | dinitrogen Environmental Molecular Sciences Laboratory INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY iron Mossbauer square planer thermodynamics |
| title | Catalytic N 2 Reduction to Silylamines and Thermodynamics of N 2 Binding at Square Planar Fe |
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