Challenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center

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dc.contributor.authorBiskup, David
dc.contributor.authorSchnakenburg, Gregor
dc.contributor.authorBoeré, René T.
dc.contributor.authorFerao, Arturo E.
dc.contributor.authorStreubel, Rainer K.
dc.date.accessioned2024-06-21T19:33:10Z
dc.date.available2024-06-21T19:33:10Z
dc.date.issued2023
dc.descriptionOpen access article. Creative Commons Attribution 4.0 International Deed license (CC BY 4.0) applies
dc.description.abstractWe 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.
dc.description.peer-reviewYes
dc.identifier.citationBiskup, D., Schnakenburg, G., Boeré, R. T., Ferao, A. E., & Streubel, R. K. (2023). Challenging an old paradign by demonstrating transition metal-like chemistry at a neutral nonmetal center. Nature Communications, 14, Article 6456. https://doi.org/10.1038/s41467-023-42127-3
dc.identifier.urihttps://hdl.handle.net/10133/6797
dc.language.isoen
dc.publisherNature Portfolio
dc.publisher.departmentDepartment of Chemistry and Biochemistry
dc.publisher.facultyArts and Science
dc.publisher.institutionUniversität Bonn
dc.publisher.institutionUniversity of Lethbridge
dc.publisher.institutionUniversidad de Murcia
dc.publisher.urlhttps://doi.org/10.1038/s41467-023-42127-3
dc.subjectChemical bonding
dc.subjectComputational chemistry
dc.subjectSynthetic chemistry methodology
dc.subjectMetal-like
dc.subjectNonmetal
dc.titleChallenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center
dc.typeArticle
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