Metal–Ligand Role Reversal: Hydride-Transfer Catalysis by a Functional Phosphorus Ligand with a Spectator Metal
Hydride transfer catalysis is shown to be enabled by the nonspectator reactivity of a transition metal-bound low-symmetry tricoordinate phosphorus ligand. Complex 1·[Ru]+, comprising a nontrigonal phosphorus chelate (1, P(N(o-N(2-pyridyl)C6H4)2) and an inert metal fragment ([Ru] = (Me5C5)Ru), r...
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| Veröffentlicht in: | Journal of the American Chemical Society 2022-11, Vol.144 (47), p.21443-21447 |
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| container_issue | 47 |
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| container_title | Journal of the American Chemical Society |
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| creator | Bruch, Quinton J. Tanushi, Akira Müller, Peter Radosevich, Alexander T. |
| description | Hydride transfer catalysis is shown to be enabled by the nonspectator reactivity of a transition metal-bound low-symmetry tricoordinate phosphorus ligand. Complex 1·[Ru]+, comprising a nontrigonal phosphorus chelate (1, P(N(o-N(2-pyridyl)C6H4)2) and an inert metal fragment ([Ru] = (Me5C5)Ru), reacts with NaBH4 to give a metallohydridophosphorane (1 H ·[Ru]) by P–H bond formation. Complex 1 H ·[Ru] is revealed to be a potent hydride donor (ΔG°H–,exp < 41 kcal/mol, ΔG°H–,calc = 38 ± 2 kcal/mol in MeCN). Taken together, the reactivity of the 1·[Ru]+/1 H ·[Ru] pair comprises a catalytic couple, enabling catalytic hydrodechlorination in which phosphorus is the sole reactive site of hydride transfer. |
| doi_str_mv | 10.1021/jacs.2c10200 |
| format | Article |
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Complex 1·[Ru]+, comprising a nontrigonal phosphorus chelate (1, P(N(o-N(2-pyridyl)C6H4)2) and an inert metal fragment ([Ru] = (Me5C5)Ru), reacts with NaBH4 to give a metallohydridophosphorane (1 H ·[Ru]) by P–H bond formation. Complex 1 H ·[Ru] is revealed to be a potent hydride donor (ΔG°H–,exp < 41 kcal/mol, ΔG°H–,calc = 38 ± 2 kcal/mol in MeCN). 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Am. Chem. Soc</addtitle><description>Hydride transfer catalysis is shown to be enabled by the nonspectator reactivity of a transition metal-bound low-symmetry tricoordinate phosphorus ligand. Complex 1·[Ru]+, comprising a nontrigonal phosphorus chelate (1, P(N(o-N(2-pyridyl)C6H4)2) and an inert metal fragment ([Ru] = (Me5C5)Ru), reacts with NaBH4 to give a metallohydridophosphorane (1 H ·[Ru]) by P–H bond formation. Complex 1 H ·[Ru] is revealed to be a potent hydride donor (ΔG°H–,exp < 41 kcal/mol, ΔG°H–,calc = 38 ± 2 kcal/mol in MeCN). Taken together, the reactivity of the 1·[Ru]+/1 H ·[Ru] pair comprises a catalytic couple, enabling catalytic hydrodechlorination in which phosphorus is the sole reactive site of hydride transfer.</description><subject>Catalysis</subject><subject>Ligands</subject><subject>Metals</subject><subject>Phosphorus</subject><subject>Transition Elements - chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkU9P2zAchq1paJQ_t50nH3cgYDuJnewwCVUwkIqGCpytX5xfqKs0LnYC6o3vsG-4TzKXFsaknfzv8fNafgn5zNkxZ4KfzMGEY2HinLEPZMRzwZKcC_mRjBhjIlGFTHfJXgjzuMxEwT-R3VSmcVvIEXm4wh7a38-_JvYeuppOXYt0io_oA7Tf6MWq9rbG5NZDFxr0dAwRXwUbaLWiQM-HzvTWddDS65kLy5nzQ6Bb15PtZ5G5WaLpoXeevmQdkJ0G2oCH23Gf3J2f3Y4vksnPH5fj00kCGVd9wkteF6zOs9zUJgMQkisDtYHCZKlREhowjahKlZeyEk2RYslEBrwoG1VxxHSffN94l0O1wNpg13to9dLbBfiVdmD1vyednel796hLxYWQIgq-bgXePQwYer2wwWDbQoduCFqoVEqZi0xF9GiDGu9C8Ni8xXCm1y3pdUt621LEv7x_2hv8Wsvf6PWtuRt8_ODwf9cfIl6eqg</recordid><startdate>20221130</startdate><enddate>20221130</enddate><creator>Bruch, Quinton J.</creator><creator>Tanushi, Akira</creator><creator>Müller, Peter</creator><creator>Radosevich, Alexander T.</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0001-6530-3852</orcidid><orcidid>https://orcid.org/0000-0002-5373-7343</orcidid><orcidid>https://orcid.org/0000-0002-3653-1036</orcidid><orcidid>https://orcid.org/0000-0002-9461-5529</orcidid></search><sort><creationdate>20221130</creationdate><title>Metal–Ligand Role Reversal: Hydride-Transfer Catalysis by a Functional Phosphorus Ligand with a Spectator Metal</title><author>Bruch, Quinton J. ; Tanushi, Akira ; Müller, Peter ; Radosevich, Alexander T.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a417t-191d80d545cdc4aa2617cadca8c43c76afacf2b97596b2f83e9024a189f7b1ee3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Catalysis</topic><topic>Ligands</topic><topic>Metals</topic><topic>Phosphorus</topic><topic>Transition Elements - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Bruch, Quinton J.</creatorcontrib><creatorcontrib>Tanushi, Akira</creatorcontrib><creatorcontrib>Müller, Peter</creatorcontrib><creatorcontrib>Radosevich, Alexander T.</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Bruch, Quinton J.</au><au>Tanushi, Akira</au><au>Müller, Peter</au><au>Radosevich, Alexander T.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Metal–Ligand Role Reversal: Hydride-Transfer Catalysis by a Functional Phosphorus Ligand with a Spectator Metal</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2022-11-30</date><risdate>2022</risdate><volume>144</volume><issue>47</issue><spage>21443</spage><epage>21447</epage><pages>21443-21447</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Hydride transfer catalysis is shown to be enabled by the nonspectator reactivity of a transition metal-bound low-symmetry tricoordinate phosphorus ligand. Complex 1·[Ru]+, comprising a nontrigonal phosphorus chelate (1, P(N(o-N(2-pyridyl)C6H4)2) and an inert metal fragment ([Ru] = (Me5C5)Ru), reacts with NaBH4 to give a metallohydridophosphorane (1 H ·[Ru]) by P–H bond formation. Complex 1 H ·[Ru] is revealed to be a potent hydride donor (ΔG°H–,exp < 41 kcal/mol, ΔG°H–,calc = 38 ± 2 kcal/mol in MeCN). 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| source | MEDLINE; American Chemical Society Journals |
| subjects | Catalysis Ligands Metals Phosphorus Transition Elements - chemistry |
| title | Metal–Ligand Role Reversal: Hydride-Transfer Catalysis by a Functional Phosphorus Ligand with a Spectator Metal |
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