Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H 2 Activation Mode
Deprotonation of the Mn NHC-phosphine complex fac-[MnBr(CO) (κ P,C-Ph PCH NHC)] (2) under a H atmosphere readily gives the hydride fac-[MnH(CO) (κ P,C-Ph PCH NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO) (κ P,C,C-Ph PCHNHC)] (6 a). DFT calculat...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2019-05, Vol.58 (20), p.6727-6731 |
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| creator | Buhaibeh, Ruqaya Filippov, Oleg A Bruneau-Voisine, Antoine Willot, Jérémy Duhayon, Carine Valyaev, Dmitry A Lugan, Noël Canac, Yves Sortais, Jean-Baptiste |
| description | Deprotonation of the Mn
NHC-phosphine complex fac-[MnBr(CO)
(κ
P,C-Ph
PCH
NHC)] (2) under a H
atmosphere readily gives the hydride fac-[MnH(CO)
(κ
P,C-Ph
PCH
NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO)
(κ
P,C,C-Ph
PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16-e mangana-substituted phosphonium ylide complex fac-[Mn(CO)
(κ
P,C-Ph
P=CHNHC)] (6 b) as key intermediate able to activate H
via a non-classical mode of metal-ligand cooperation implying a formal λ
-P-λ
-P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre-catalysts for ketone hydrogenation in the Mn
series reported to date (TON up to 6200). |
| doi_str_mv | 10.1002/anie.201901169 |
| format | Article |
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NHC-phosphine complex fac-[MnBr(CO)
(κ
P,C-Ph
PCH
NHC)] (2) under a H
atmosphere readily gives the hydride fac-[MnH(CO)
(κ
P,C-Ph
PCH
NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO)
(κ
P,C,C-Ph
PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16-e mangana-substituted phosphonium ylide complex fac-[Mn(CO)
(κ
P,C-Ph
P=CHNHC)] (6 b) as key intermediate able to activate H
via a non-classical mode of metal-ligand cooperation implying a formal λ
-P-λ
-P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre-catalysts for ketone hydrogenation in the Mn
series reported to date (TON up to 6200).</description><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201901169</identifier><identifier>PMID: 30860308</identifier><language>eng</language><publisher>Germany</publisher><ispartof>Angewandte Chemie International Edition, 2019-05, Vol.58 (20), p.6727-6731</ispartof><rights>2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c192t-8d57e009773f324fb59696c2f54f4c16c2445fb188d7021a22d82faa6fdc30783</citedby><cites>FETCH-LOGICAL-c192t-8d57e009773f324fb59696c2f54f4c16c2445fb188d7021a22d82faa6fdc30783</cites><orcidid>0000-0002-3744-5252 ; 0000-0002-1772-844X ; 0000-0003-1178-8588 ; 0000-0002-3747-554X ; 0000-0002-7963-2806 ; 0000-0001-7345-8782 ; 0000-0002-0984-3261</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/30860308$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Buhaibeh, Ruqaya</creatorcontrib><creatorcontrib>Filippov, Oleg A</creatorcontrib><creatorcontrib>Bruneau-Voisine, Antoine</creatorcontrib><creatorcontrib>Willot, Jérémy</creatorcontrib><creatorcontrib>Duhayon, Carine</creatorcontrib><creatorcontrib>Valyaev, Dmitry A</creatorcontrib><creatorcontrib>Lugan, Noël</creatorcontrib><creatorcontrib>Canac, Yves</creatorcontrib><creatorcontrib>Sortais, Jean-Baptiste</creatorcontrib><title>Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H 2 Activation Mode</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Deprotonation of the Mn
NHC-phosphine complex fac-[MnBr(CO)
(κ
P,C-Ph
PCH
NHC)] (2) under a H
atmosphere readily gives the hydride fac-[MnH(CO)
(κ
P,C-Ph
PCH
NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO)
(κ
P,C,C-Ph
PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16-e mangana-substituted phosphonium ylide complex fac-[Mn(CO)
(κ
P,C-Ph
P=CHNHC)] (6 b) as key intermediate able to activate H
via a non-classical mode of metal-ligand cooperation implying a formal λ
-P-λ
-P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre-catalysts for ketone hydrogenation in the Mn
series reported to date (TON up to 6200).</description><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNo9kM1OAjEYRRujEUS3Lk1foNif-eksyQTFBNCFriffTFuoGdrJdCTy9pSgbPrdxb0n6UHokdEpo5Q_g7N6yikrKGNZcYXGLOWMiDwX1zEnQpBcpmyE7kL4jn0paXaLRoLKjMZnjPYfWx-6rXWarBclXoHbgNNB48VB9X6jHQzWO1zCAO0hDHj-u7W1HazbYMBr70jZQgi2gRavdOyQpY0AhUvvO93H8T6iMMezJsYza-WVvkc3BtqgH_7uBH29zD_LBVm-v76VsyVpWMEHIlWaa0qL-B0jeGLqtMiKrOEmTUzSsJiSJDU1k1LllDPgXEluADKjGkFzKSZoeuY2vQ-h16bqeruD_lAxWp0EVieB1UVgHDydB91PvdPqUv83Jo7N0Gxc</recordid><startdate>20190513</startdate><enddate>20190513</enddate><creator>Buhaibeh, Ruqaya</creator><creator>Filippov, Oleg A</creator><creator>Bruneau-Voisine, Antoine</creator><creator>Willot, Jérémy</creator><creator>Duhayon, Carine</creator><creator>Valyaev, Dmitry A</creator><creator>Lugan, Noël</creator><creator>Canac, Yves</creator><creator>Sortais, Jean-Baptiste</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-3744-5252</orcidid><orcidid>https://orcid.org/0000-0002-1772-844X</orcidid><orcidid>https://orcid.org/0000-0003-1178-8588</orcidid><orcidid>https://orcid.org/0000-0002-3747-554X</orcidid><orcidid>https://orcid.org/0000-0002-7963-2806</orcidid><orcidid>https://orcid.org/0000-0001-7345-8782</orcidid><orcidid>https://orcid.org/0000-0002-0984-3261</orcidid></search><sort><creationdate>20190513</creationdate><title>Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H 2 Activation Mode</title><author>Buhaibeh, Ruqaya ; Filippov, Oleg A ; Bruneau-Voisine, Antoine ; Willot, Jérémy ; Duhayon, Carine ; Valyaev, Dmitry A ; Lugan, Noël ; Canac, Yves ; Sortais, Jean-Baptiste</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c192t-8d57e009773f324fb59696c2f54f4c16c2445fb188d7021a22d82faa6fdc30783</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Buhaibeh, Ruqaya</creatorcontrib><creatorcontrib>Filippov, Oleg A</creatorcontrib><creatorcontrib>Bruneau-Voisine, Antoine</creatorcontrib><creatorcontrib>Willot, Jérémy</creatorcontrib><creatorcontrib>Duhayon, Carine</creatorcontrib><creatorcontrib>Valyaev, Dmitry A</creatorcontrib><creatorcontrib>Lugan, Noël</creatorcontrib><creatorcontrib>Canac, Yves</creatorcontrib><creatorcontrib>Sortais, Jean-Baptiste</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Buhaibeh, Ruqaya</au><au>Filippov, Oleg A</au><au>Bruneau-Voisine, Antoine</au><au>Willot, Jérémy</au><au>Duhayon, Carine</au><au>Valyaev, Dmitry A</au><au>Lugan, Noël</au><au>Canac, Yves</au><au>Sortais, Jean-Baptiste</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H 2 Activation Mode</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2019-05-13</date><risdate>2019</risdate><volume>58</volume><issue>20</issue><spage>6727</spage><epage>6731</epage><pages>6727-6731</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Deprotonation of the Mn
NHC-phosphine complex fac-[MnBr(CO)
(κ
P,C-Ph
PCH
NHC)] (2) under a H
atmosphere readily gives the hydride fac-[MnH(CO)
(κ
P,C-Ph
PCH
NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO)
(κ
P,C,C-Ph
PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16-e mangana-substituted phosphonium ylide complex fac-[Mn(CO)
(κ
P,C-Ph
P=CHNHC)] (6 b) as key intermediate able to activate H
via a non-classical mode of metal-ligand cooperation implying a formal λ
-P-λ
-P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre-catalysts for ketone hydrogenation in the Mn
series reported to date (TON up to 6200).</abstract><cop>Germany</cop><pmid>30860308</pmid><doi>10.1002/anie.201901169</doi><tpages>5</tpages><orcidid>https://orcid.org/0000-0002-3744-5252</orcidid><orcidid>https://orcid.org/0000-0002-1772-844X</orcidid><orcidid>https://orcid.org/0000-0003-1178-8588</orcidid><orcidid>https://orcid.org/0000-0002-3747-554X</orcidid><orcidid>https://orcid.org/0000-0002-7963-2806</orcidid><orcidid>https://orcid.org/0000-0001-7345-8782</orcidid><orcidid>https://orcid.org/0000-0002-0984-3261</orcidid></addata></record> |
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| title | Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H 2 Activation Mode |
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