Strong Evidence for an Unprecedented Borderline Case of Dissociation and Cycloaddition in Open‐Shell 1,3‐Dipole Chemistry: Transient Nitrilium Phosphane‐Ylide Complex Radical Cations

Abstract

Keywords: Density functional calculations / Electron transfer / Single electron transfer reactions / Radical ions / HSAB parametersThe reaction of 3-ferrocenyl-substituted 2H-azaphosphirene complexes 1a-c in the presence of substoichiometric amounts of ferrocenium hexafluorophosphate yields 3,5-diferrocenylsubstituted 2H-1,4,2-diazaphosphole complexes 3a-c and difluoro(organo)phosphane complexes 4a-c. The reaction of 1a,c and [FcH]PF 6 with cyanoferrocene yields 3a,c in a straightforward way. The molecular structures of 3a,c were unambiguously identified by multinuclear NMR spectroscopic experiments, mass spectrometry, and single-crystal Xray diffraction studies. DFT calculations on model complexes

Comparative Computational Study on the Reaction of Chloroacetone with Trimethylphosphite: Perkow versus Michaelis–Arbuzov Reaction Paths

“…According to the HSAB principle, two interacting acid–base sites should have local softness as close as possible. In other words, a molecule B will preferentially interact with another molecule A containing several potential interaction sites A j ( j = 1, 2, ...) by using the site that yields the lowest possible quadratic difference in softness, Δ s j 2 , eq . , The same was more recently shown to be true for the quadratic difference in philicity, Δω j 2 , eq . , …”

Terminal Phosphinidene Complex Adducts with Neutral and Anionic O-Donors and Halides and the Search for a Differentiating Bonding Descriptor

“…A rather different focus is the coordination chemistry of ligands L to the phosphorus center of complexes I , leading to adducts II (Figure ). As early as 1997, a related ligand-exchange phenomenon in transiently formed nitrilium phosphane-ylide complexes [(CO) 5 M­{P­(NCR′)­R}] ( II ) was reported and then termed transylidation . Also, preliminary results on the reactivity of I toward π ligands and, particularly, heterocumulenes [carbon dioxide (CO 2 ) and isocyanates] were reported.…”

Analysis of Non‐innocence of Phosphaquinodimethane Ligands when Charge and Aromaticity Come into Play

“…Worth is mentioning that all complexes 2b M give a good (almost linear) second‐order polynomial fit of IP against HOMQc8 (Figure 6), with a clear dependency of IP on the P‐substituent in the order 2bI M > 2bIII M > 2bII M . No clear metal‐dependency is observed, in stark contrast to the observed ease of oxidation for [M(CO) 5 (PR 3 )] [1c] or related phosphorus three‐ and five‐mem‐bered heterocyclic complexes [28] . Obviously, the unligated species 1 b show a different behaviour due to their extra lone pair being involved in the ionization process.…”

“…No clear metal‐dependency is observed, in stark contrast to the observed ease of oxidation for [M(CO) 5 (PR 3 )] [1c] or related phosphorus three‐ and five‐mem‐bered heterocyclic complexes. [28] Obviously, the unligated species 1 b show a different behaviour due to their extra lone pair being involved in the ionization process.…”