The synthesis of sterically demanding 2,6‐bis(2,4,6‐trimethylphenyl)phenyl (Ter)‐stabilized potassium phosphinophosphido dithioformates 1a–b K[TerP(CS 2 )PR 2 ] via conversion of the corresponding potassium phosphinophosphides K[TerP–PR 2 ] (R = i Pr, t Bu) with CS 2 is reported. In solution, the dithioformates 1a–b undergo a migration reaction, resulting in the formation of anionic phosphanylthioketones, K[TerPC(=S)–P(S)R 2 ] ( 2a‐b ), bearing phosphanylthiolate groups. The cocrystallization of compounds 1a and 2…

Starting from the biradicaloid [ · P(μ‐NTer) 2 P·] (Ter = 2,6‐dimesitylphenyl), the addition of ethyl bromide yields the addition product [Et–P(μ‐NTer) 2 P–Br]. Using 1,6‐dibromohexane, the corresponding hexyl‐bridged species [Br–P(μ‐NTer) 2 P–hexyl–P(μ‐NTer) 2 P–Br] is formed. The addition of one or two equivalents of a strong Lewis acid such as GaCl 3 leads to the abstraction of the bromide, forming the monocation [Et–P(μ‐NTer) 2 P] + or the dication [P(μ‐NTer) 2 P–hexyl–P(μ‐NTer) 2 P] 2+ , respectively. Both ne…

Abstract The reactions of Pacman phosphanes ( 1a ) with Lewis acids such as R 3 B (R = C 6 H 5 , C 6 F 5 ) and GaCl 3 were investigated. While equilibria between mono‐ and di‐adducts were found in the reaction with BPh 3 , B(C 6 F 5 ) 3 preferentially formed the di‐adduct ( 1a· 2B(C 6 F 5 ) 3 ), which could be isolated and fully characterized. density functional theory (DFT) calculations showed that the N ‐bonded adducts are thermodynamically more stable than the P ‐bonded adducts. In contrast to the reaction of t…

Abstract The linkage of an imidazole‐based N ‐heterocyclic olefin (NHO), containing a terminal CH 2 donor group, with a phosphorus‐centered diradical molecular fragment leads to an open‐shell singlet diphospha‐indenylide system, a new class of P ‐heterocycles, which can be interpreted both as a phosphorus‐centered diradicaloid and as a zwitterion with a permanent, overall charge separation between the N ‐ and P ‐heterocyclic ring systems. The rotation of the imidazole ring, which is thermally possible due to a cen…

We show that photoswitching of an organic biradicaloid into its inactive housane form allows for light-controlled spin hyperpolarization in the metal-free activation of parahydrogen.