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

David Biskup, Gregor Schnakenburg, René T. Boeré, Arturo Espinosa Ferao () and Rainer K. Streubel ()
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David Biskup: Rheinische Friedrich-Wilhelms-Universität Bonn
Gregor Schnakenburg: Rheinische Friedrich-Wilhelms-Universität Bonn
René T. Boeré: University of Lethbridge
Arturo Espinosa Ferao: Universidad de Murcia
Rainer K. Streubel: Rheinische Friedrich-Wilhelms-Universität Bonn

Nature Communications, 2023, vol. 14, issue 1, 1-13

Abstract: 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.

Date: 2023
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DOI: 10.1038/s41467-023-42127-3

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