Combining geometric constraint and redox non-innocence within an ambiphilic PBiP pincer ligand
The synthesis of the first pincer ligand featuring a strictly T-shaped group 15 element and its coordination behaviour towards transition metals is described. The platform is itself derived from a trianionic redox non-innocent NNN scaffold. In addition to providing a rigid coordination environment t...
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| Veröffentlicht in: | Chemical science (Cambridge) 2024-04, Vol.15 (16), p.636-643 |
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| creator | Coburger, Peter Buzanich, Ana Guilherme Emmerling, Franziska Abbenseth, Josh |
| description | The synthesis of the first pincer ligand featuring a strictly T-shaped group 15 element and its coordination behaviour towards transition metals is described. The platform is itself derived from a trianionic redox non-innocent NNN scaffold. In addition to providing a rigid coordination environment to constrain a Bi centre in a T-shaped geometry to manipulate its frontier molecular orbital constitution, the NNN chelate displays highly covalent bonding towards the geometrically constrained Bi centre. The formation of intriguing ambiphilic Bi-M bonding interactions is demonstrated upon formation of a pincer complex as well as a multimetallic cluster. All compounds are comprehensively characterised by spectroscopic methods including X-ray Absorption Near Edge Structure (XANES) spectroscopy and complemented by DFT calculations.
The first pincer ligand featuring a strictly T-shaped pnictogen donor moiety was synthesised. The PBiP ligand's redox activity facilitates unprecedented ambiphilic bonding of the Bi centre with transition metals through the Bi(6p) orbital. |
| doi_str_mv | 10.1039/d4sc00197d |
| format | Article |
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The first pincer ligand featuring a strictly T-shaped pnictogen donor moiety was synthesised. The PBiP ligand's redox activity facilitates unprecedented ambiphilic bonding of the Bi centre with transition metals through the Bi(6p) orbital.</description><subject>Chemistry</subject><subject>Coordination</subject><subject>Geometric constraints</subject><subject>Ligands</subject><subject>Molecular orbitals</subject><subject>T shape</subject><subject>Transition metals</subject><subject>X ray absorption</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNpdkd2LEzEUxYModun2xXcl4IsszJqvyTRPoq26QsGC-mq4k2TaLDNJTaa763-_WVvrR14SOL9zOTcHoWeUXFLC1WsrsiGEqsY-QmeMCFrJmqvHpzcjEzTL-ZqUwzmtWfMUTfhcyrpgZ-j7Ig6tDz5s8MbFwY3JG2xiyGMCH0YMweLkbLzDIYbKhxCNC8bhWz9ufSgyhuLfbX1ffOt3fo13vugJ935TvOfoSQd9drPjPUXfPrz_uriqVp8_flq8XVVGMDVW0NhaUqDEQddJZ42ShlrZAggLriSnjWoVMAG2bYF3zgCjomFCGTNvoeVT9OYwd7dvh-J3oeTv9S75AdJPHcHrf5Xgt3oTbzSlRBApRJnw6jghxR97l0c9-Gxc30NwcZ81J6JRYi7KL07Ry__Q67hPoez3QAnWsJrJQl0cKJNizsl1pzSU6Ifq9FJ8WfyqblngF3_nP6G_iyrA8wOQsjmpf7rn93H1oBI</recordid><startdate>20240424</startdate><enddate>20240424</enddate><creator>Coburger, Peter</creator><creator>Buzanich, Ana Guilherme</creator><creator>Emmerling, Franziska</creator><creator>Abbenseth, Josh</creator><general>Royal Society of Chemistry</general><general>The Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-8787-6253</orcidid><orcidid>https://orcid.org/0000-0001-5543-9924</orcidid><orcidid>https://orcid.org/0000-0001-8528-0301</orcidid></search><sort><creationdate>20240424</creationdate><title>Combining geometric constraint and redox non-innocence within an ambiphilic PBiP pincer ligand</title><author>Coburger, Peter ; Buzanich, Ana Guilherme ; Emmerling, Franziska ; Abbenseth, Josh</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c429t-a7d561a10eaff6edc96c1d6baa4dae000179b9a24adbba3feca2147249cc8bab3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Chemistry</topic><topic>Coordination</topic><topic>Geometric constraints</topic><topic>Ligands</topic><topic>Molecular orbitals</topic><topic>T shape</topic><topic>Transition metals</topic><topic>X ray absorption</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Coburger, Peter</creatorcontrib><creatorcontrib>Buzanich, Ana Guilherme</creatorcontrib><creatorcontrib>Emmerling, Franziska</creatorcontrib><creatorcontrib>Abbenseth, Josh</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Coburger, Peter</au><au>Buzanich, Ana Guilherme</au><au>Emmerling, Franziska</au><au>Abbenseth, Josh</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Combining geometric constraint and redox non-innocence within an ambiphilic PBiP pincer ligand</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2024-04-24</date><risdate>2024</risdate><volume>15</volume><issue>16</issue><spage>636</spage><epage>643</epage><pages>636-643</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>The synthesis of the first pincer ligand featuring a strictly T-shaped group 15 element and its coordination behaviour towards transition metals is described. The platform is itself derived from a trianionic redox non-innocent NNN scaffold. In addition to providing a rigid coordination environment to constrain a Bi centre in a T-shaped geometry to manipulate its frontier molecular orbital constitution, the NNN chelate displays highly covalent bonding towards the geometrically constrained Bi centre. The formation of intriguing ambiphilic Bi-M bonding interactions is demonstrated upon formation of a pincer complex as well as a multimetallic cluster. All compounds are comprehensively characterised by spectroscopic methods including X-ray Absorption Near Edge Structure (XANES) spectroscopy and complemented by DFT calculations.
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| subjects | Chemistry Coordination Geometric constraints Ligands Molecular orbitals T shape Transition metals X ray absorption |
| title | Combining geometric constraint and redox non-innocence within an ambiphilic PBiP pincer ligand |
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