A Triazadiphosphole

Staudinger Reaction as a Way Out To Avoid Cyclization in the Reaction of Silylated Dichloro(hydrazino)phosphane with Trimethylsilyl Azide

“…Trimethylsilyl azide (98 %, Fluka) was distilled freshly prior to use, GaCl 3 (99.99 %, Sigma-Aldrich) was used as received. 1 X-ray Structure Determination: A X-ray quality crystal of 2 was selected at -50°C in Galden HT230 oil (Solvay Solexis) and mounted on a glass fibre in a low-temperature N 2 stream. A suitable crystal of compound 1 was selected in Kel-F oil (Riedel de Haen) at room temperature.…”

“…[1] Access to this new class of neutral binary nitrogen-phosphorus heterocycles was gained by GaCl 3 assisted [3+2] cycloaddition reactions, in which GaCl 3 triggers TMSCl elimination in suitable precursors, releasing the dipolarophile and/or the 1,3-dipole, and finally stabilizes the formed, labile heterocycle by adduct formation. [2] For instance, the GaCl 3 assisted [2+3] cycloaddition of Mes*-N=P-Cl with trimethylsilyl azide (TMSN 3 ) results in the formation of a tetrazaphosphole kinetically stabilized as a GaCl 3 adduct in high yields (Scheme 1).…”

The potential energy surface of the triazadiphosphole formation

“…Recently, GaCl 3 -assisted elimination reactions in main group compounds have attracted considerable interest [1][2][3][4]. In these reactions GaCl 3 is responsible for two important things: (i) decreasing of the activation barrier to elimination [5] and (ii) stabilization of labile main group species e.g., azaphospholes by adduct formation (Scheme 1) [1][2][3][4].…”

“…In these reactions GaCl 3 is responsible for two important things: (i) decreasing of the activation barrier to elimination [5] and (ii) stabilization of labile main group species e.g., azaphospholes by adduct formation (Scheme 1) [1][2][3][4]. Furthermore, GaCl 3 adduct formation seems to be the key to kinetic stabilization of thermodynamic instable intermediates.…”

“…Furthermore, GaCl 3 adduct formation seems to be the key to kinetic stabilization of thermodynamic instable intermediates. In this article we have studied the mechanism of the formation of the five-membered ring in triazadiphospholes (Scheme 1) starting from N,N 0 ,N 0 -[tris(trimethylsilyl)]hydrazine(dichloro)phosphane, (Me 3 Si) 2 N-(Me 3 Si)N-PCl 2 (1).…”