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

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Biskup, David
Schnakenburg, Gregor
Boeré, René T.
Ferao, Arturo E.
Streubel, Rainer K.
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Nature Portfolio
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.
Open access article. Creative Commons Attribution 4.0 International Deed license (CC BY 4.0) applies
Chemical bonding , Computational chemistry , Synthetic chemistry methodology , Metal-like , Nonmetal
Biskup, 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.