Stable Heterocyclopentane‐1,3‐diyls

Abstract

Diphosphadiazanediyl, [(μ-NR)P]2 (R=Ter=2,6-dimesitylphenyl), is known to readily activate small molecules with multiple bonds. CO is an especially intriguing species for activation, because either 1,1- or 1,2-bridging mode would lead to a [1.1.1]bicycle or a carbene, respectively. The activation of CO with diphosphadiazanediyl already occurs at ambient temperatures (1 bar, 25 °C). However, CO is involved in an unprecedented ring expansion reaction under preservation of the biradical character, which leads to the formation of the first stable cyclopentane-1,3-diyl analogue displaying photochromic molecular switch characteristics.

Cyclic Group 15 Radical Cations

“…[34][35][36] Since in the mass spectra of the biradicaloids [P(m-NTer) 2 P] (2P 2 ), [P(m-NTer) 2 As] (2PAs), and [As(m-NTer) 2 As] (2As 2 )t he corresponding molecular cations (3 + C)c ould be detected (m/z 716, 760, 804) with surprisingly high intensities,wewere intrigued by the idea to carry out the selective oxidation of the dipnictadiazane-1,3diyls 2 yielding the 5p electrons containing radical cations 3 + C as shown in Scheme 2. [34][35][36] Since in the mass spectra of the biradicaloids [P(m-NTer) 2 P] (2P 2 ), [P(m-NTer) 2 As] (2PAs), and [As(m-NTer) 2 As] (2As 2 )t he corresponding molecular cations (3 + C)c ould be detected (m/z 716, 760, 804) with surprisingly high intensities,wewere intrigued by the idea to carry out the selective oxidation of the dipnictadiazane-1,3diyls 2 yielding the 5p electrons containing radical cations 3 + C as shown in Scheme 2.…”

Tunable Cyclopentane-1,3-diyls Generated by Insertion of Isonitriles into Diphosphadiazanediyls

“…35 Our group recently reported on the activation of CO by cyclodiphosphadiazanediyl (1), [P(µ-NTer)] 2 , that lead to the isolation of the first stable cyclopentane-1,3-diyl derivative with a P 2 N 2 C five-membered heterocycle and an exocyclic CO functionality (Scheme 2, species H). 36,37 Since isonitriles (2) show similar electronic properties to CO, but allow tuning of the electronic properties by different substitution, we were intrigued by the idea to study the activation of isonitriles by cyclodiphosphadiazanediyls (1,Scheme 4). In this contribution, we present our results with respect to the activation of isonitriles, which depends on the steric influence of its organic substituent.…”

“…36 Thus we studied the influence of irradiation on biradicaloids 3 and tetraradicaloid 10 by means of 31 P NMR experiments. 3 t Bu already formed the housane species 3' t Bu in small amounts under daylight, while dark blue 3Dmp revealed the formation of colorless 3'Dmp only under uv irradiation (Scheme 10).…”

“…Thus with progressing measuring time the crystals became slowly colorless indicating decomposition, an effect already known from [Ter 2 N 2 P 2 CO] (species H, Scheme 2). 36 This phenomenon always resulted in poor X-ray diffraction data sets, which just allowed the confirmation of the connectivity, but no detailed discussion of the molecular geometry ( Figure 1). Interestingly, the computationally optimized structures 44 agree nicely with the (poor) experimental data.…”

Anorganische Molekülchemie

“…Die stark -acide Verbindung (NHC)InBr 2 (SbF 6 ) entsteht ausgehend von (NHC)InBr 3 und AgSbF 6 , sie zeigt katalytische Aktivität in Hydroarylierungs-, Transferhydrierungs-und Cycloisomerisierungsreaktionen. 24 (57). 53 Mit dem Begriff Aromatizität assoziieren Chemiker meist Verbindungen der organischen Chemie.…”