Challenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center
Abstract We describe nonmetal adducts of the phosphorus center of terminal phosphinidene complexes using classical C- and N-ligands from metal coordination chemistry. The nature of the L-P bond has been analyzed by various theoretical methods including a refined method on the variation of the Laplac...
| Main Authors: | , , , , |
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| Format: | Article |
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Nature Portfolio
2023-10-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-42127-3 |
| _version_ | 1797558510992490496 |
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| author | David Biskup Gregor Schnakenburg René T. Boeré Arturo Espinosa Ferao Rainer K. Streubel |
| author_facet | David Biskup Gregor Schnakenburg René T. Boeré Arturo Espinosa Ferao Rainer K. Streubel |
| author_sort | David Biskup |
| collection | DOAJ |
| description | Abstract We describe nonmetal adducts of the phosphorus center of terminal phosphinidene complexes using classical C- and N-ligands from metal coordination chemistry. The nature of the L-P bond has been analyzed by various theoretical methods including a refined method on the variation of the Laplacian of electron density ∇2ρ along the L-P bond path. Studies on thermal stability reveal stark differences between N-ligands such as N-methyl imidazole and C-ligands such as tert-butyl isocyanide, including ligand exchange reactions and a surprising formation of white phosphorus. A milestone is the transformation of a nonmetal-bound isocyanide into phosphaguanidine or an acyclic bisaminocarbene bound to phosphorus; the latter is analogous to the chemistry of transition metal-bound isocyanides, and the former reveals the differences. This example has been studied via cutting-edge DFT calculations leading to two pathways differently favored depending on variations in steric demand. This study reveals the emergence of organometallic from coordination chemistry of a neutral nonmetal center. |
| first_indexed | 2024-03-10T17:32:24Z |
| format | Article |
| id | doaj.art-3b2fd2e04f584d86b71f8d95875defba |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-10T17:32:24Z |
| publishDate | 2023-10-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-3b2fd2e04f584d86b71f8d95875defba2023-11-20T09:58:18ZengNature PortfolioNature Communications2041-17232023-10-0114111310.1038/s41467-023-42127-3Challenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal centerDavid Biskup0Gregor Schnakenburg1René T. Boeré2Arturo Espinosa Ferao3Rainer K. Streubel4Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität BonnInstitut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität BonnDepartment of Chemistry and Biochemistry, University of LethbridgeDepartamento de Química Orgánica, Facultad de Química, Campus de Espinardo, Universidad de MurciaInstitut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität BonnAbstract We describe nonmetal adducts of the phosphorus center of terminal phosphinidene complexes using classical C- and N-ligands from metal coordination chemistry. The nature of the L-P bond has been analyzed by various theoretical methods including a refined method on the variation of the Laplacian of electron density ∇2ρ along the L-P bond path. Studies on thermal stability reveal stark differences between N-ligands such as N-methyl imidazole and C-ligands such as tert-butyl isocyanide, including ligand exchange reactions and a surprising formation of white phosphorus. A milestone is the transformation of a nonmetal-bound isocyanide into phosphaguanidine or an acyclic bisaminocarbene bound to phosphorus; the latter is analogous to the chemistry of transition metal-bound isocyanides, and the former reveals the differences. This example has been studied via cutting-edge DFT calculations leading to two pathways differently favored depending on variations in steric demand. This study reveals the emergence of organometallic from coordination chemistry of a neutral nonmetal center.https://doi.org/10.1038/s41467-023-42127-3 |
| spellingShingle | David Biskup Gregor Schnakenburg René T. Boeré Arturo Espinosa Ferao Rainer K. Streubel Challenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center Nature Communications |
| title | Challenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center |
| title_full | Challenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center |
| title_fullStr | Challenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center |
| title_full_unstemmed | Challenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center |
| title_short | Challenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center |
| title_sort | challenging an old paradigm by demonstrating transition metal like chemistry at a neutral nonmetal center |
| url | https://doi.org/10.1038/s41467-023-42127-3 |
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