Genuine heterocycles from the acid-induced cyclization of (silylamino)(imino)(chalcogeno)phosphoranes and as a result of chloride ion abstraction from bis[bis(trimethylsilyl)amino]thiophosphoryl chloride

Nucleophilic Addition of CH, NH, and OH Bonds to the Phosphadiazonium Cation and Interpretation of 31P Chemical Shifts at Dicoordinate Phosphorus Centers

“…1,3-Hydrogen migrations, as well as the related methyl and trimethylsilyl migrations, , have been documented for neutral iminophosphines as well as a metalloiminophosphine but are usually facilitated by an external base or by heating, except in the case of Mes*N(H)PNMes* . The facile nature of the 1,3-hydrogen migration for Mes*N(H)PNMes* is confirmed by a 15 N-labeling study.…”

Cyclic phosphenium and arsenium cations with 6π electrons and related systems

“…10 It has been observed previously that such anion-cation interactions have little or no effect on the structural features within the cation or anion. 11 Indeed, the structural features of 1a derived from either the germanium exchange or metathetical route are identical within experimental error. Interestingly, the P-Cl distance in the corresponding C-C saturated analogue, 3a [2.425(4) Å] is also longer than that of typical P-Cl bonds but shorter than that in 1a thus implying that this compound is partway along the P-Cl heterolysis pathway.…”

Preparation and Characterization of P2BCh Ring Systems (Ch=S, Se) and Their Reactivity with N‐Heterocyclic Carbenes

“…[18,24,25] Moreover,s mall phosphoruschalcogen heterocycles that displaya symmetryw ithr espect to the 4-membered core are even rarer.T hese include P-S-P-E (Figure 2, G), [26][27][28] P-Ch-P-C (Ch=S, Se, H), [29][30][31] P-S-C-S (I), [32] and P-S-C-C structures (J), [33] amongst others. [34][35][36][37][38][39] Small ring cores that contain asymmetry in the presence of aP ÀPb ond are by far the rarest, with published examples limited to only three species: P-P-C-N (K), [40] P-P-C-O (L), [37] and P-P-Si-N (M). [41] In this context, we report the synthesis of small main group heterocycles containing aP 2 BCh core (3Ch;C h =S, Se) that possess aP ÀPb ond.…”

“…Moreover, small phosphorus‐chalcogen heterocycles that display asymmetry with respect to the 4‐membered core are even rarer. These include P‐S‐P‐E (Figure , G ), P‐Ch‐P‐C (Ch=S, Se, H ), P‐S‐C‐S ( I ), and P‐S‐C‐C structures ( J ), amongst others . Small ring cores that contain asymmetry in the presence of a P−P bond are by far the rarest, with published examples limited to only three species: P‐P‐C‐N ( K ), P‐P‐C‐O ( L ), and P‐P‐Si‐N ( M ) .…”