Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds
© Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P^P-chelating ligand (L1), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(o-N(Ar)C6H4)2, tethered by a phenylene linker to a -PiPr2 anchor, with group 10 complexes L...
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2022
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| Online Access: | https://hdl.handle.net/1721.1/141227.2 |
| _version_ | 1826205985594671104 |
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| author | Hwang, Seung Jun Tanushi, Akira Radosevich, Alexander T. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Hwang, Seung Jun Tanushi, Akira Radosevich, Alexander T. |
| author_sort | Hwang, Seung Jun |
| collection | MIT |
| description | © Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P^P-chelating ligand (L1), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(o-N(Ar)C6H4)2, tethered by a phenylene linker to a -PiPr2 anchor, with group 10 complexes L2M(Me)Cl (M = Ni, Pd) results in insertion of the nontrigonal phosphorus site into the metal-methyl bond. The stable methylmetallophosphorane compounds thus formed are characterized spectroscopically and crystallographically. Metalation of L1 with (cod)PtII(Me)(Cl) does not lead to a metallophosphorane but rather to the standard bisphosphine chelate (κ2-L1)Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M-C bond enthalpies. |
| first_indexed | 2024-09-23T13:22:31Z |
| format | Article |
| id | mit-1721.1/141227.2 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T13:22:31Z |
| publishDate | 2022 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/141227.22024-06-04T19:45:35Z Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds Hwang, Seung Jun Tanushi, Akira Radosevich, Alexander T. Massachusetts Institute of Technology. Department of Chemistry © Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P^P-chelating ligand (L1), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(o-N(Ar)C6H4)2, tethered by a phenylene linker to a -PiPr2 anchor, with group 10 complexes L2M(Me)Cl (M = Ni, Pd) results in insertion of the nontrigonal phosphorus site into the metal-methyl bond. The stable methylmetallophosphorane compounds thus formed are characterized spectroscopically and crystallographically. Metalation of L1 with (cod)PtII(Me)(Cl) does not lead to a metallophosphorane but rather to the standard bisphosphine chelate (κ2-L1)Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M-C bond enthalpies. 2022-06-15T13:52:35Z 2022-03-16T17:06:40Z 2022-06-15T13:52:35Z 2020-12 2020-10 2022-03-16T16:59:41Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 https://hdl.handle.net/1721.1/141227.2 Hwang, Seung Jun, Tanushi, Akira and Radosevich, Alexander T. 2020. "Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds." Journal of the American Chemical Society, 142 (51). en http://dx.doi.org/10.1021/jacs.0c11161 Journal of the American Chemical Society Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/octet-stream American Chemical Society (ACS) PMC |
| spellingShingle | Hwang, Seung Jun Tanushi, Akira Radosevich, Alexander T. Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds |
| title | Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds |
| title_full | Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds |
| title_fullStr | Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds |
| title_full_unstemmed | Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds |
| title_short | Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds |
| title_sort | enthalpy controlled insertion of a nonspectator tricoordinate phosphorus ligand into group 10 transition metal carbon bonds |
| url | https://hdl.handle.net/1721.1/141227.2 |
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