Concerted addition of aldehydes to the singlet biradical [P(μ-NTer)]₂

Abstract

The reaction of the singlet biradical [P(μ-NTer)]2 with various aldehydes selectively yielded the corresponding [2.1.1]-bicyclic addition products in a very fast reaction. All products were fully characterized, including NMR and...

Heteroatom-Based Diradical(oid)s

“…Experimentally, the reaction of 14 Ter was studied not only with formaldehyde but also with a series of different aldehydes. 333 As depicted in Figure 13, the symmetry of the frontier orbitals indicates a concerted mechanism for the addition of formaldehyde to 14 H . Another indicator of the presence of a concerted reaction mechanism is found in the cyclic structure of the transition state, as illustrated in Figure 14. A closer look at the reaction path shows that, before the actual addition to 14 H , a very weakly bound van der Waals complex is predicted, from which a cyclic transition state (TS) is formed before the addition products can be generated (Figure 14).…”

“…All products were experimentally isolated and fully characterized. Reproduced with permission from ref . Copyright 2022 Royal Society of Chemistry.…”

“…This is exemplified for the symmetry-allowed [2 + 2] addition of formaldehyde, H 2 CO, to the diradicaloid 14 H (Figure ). Experimentally, the reaction of 14 Ter was studied not only with formaldehyde but also with a series of different aldehydes . As depicted in Figure , the symmetry of the frontier orbitals indicates a concerted mechanism for the addition of formaldehyde to 14 H .…”

“…Computed at the DLPNO-CCSD­(T)/def2-QZVPP//CCSD­(T)/def2-TZVP level of theory. Reproduced with permission from ref . Copyright 2022 Royal Society of Chemistry.…”

“…Schematic representation of the interaction of the frontier MOs of the model system 14 H ( D 2 h symmetry) and H 2 CO ( C 2 v ). Reproduced with permission from ref . Copyright 2022 Royal Society of Chemistry.…”