GaCl₃-Assisted Cyclization Reactions in Hypersilyl(trimethylsilyl)aminodichlorophosphine

Abstract

Hypersilyl(trimethylsilyl)aminodichlorophosphine, (hyp)N(SiMe3)PCl2, was treated with GaCl3, which resulted in the formation of an interesting novel bicycle, composed of a four-membered SiNP2 ring and a five-membered P2Ga2Cl ring. In the presence of Me3SiN3, the same reaction provided access to a cyclo-2-phospha-4-sila-1,3-diazenium tetrachlorogallate. The free chloro-cyclo-phosphasiladiazane was obtained by the addition of nucleophilic bases.

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

“…[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. Compounds 3Ch were preparedt hrough the combination of monomeric phosphinidene chalcogenides (Ar*P=Ch)a nd phosphaborenes (Mes*P=BNR 2 )v ia formation of aP ÀPb ond.…”

“…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 ) . In this context, we report the synthesis of small main group heterocycles containing a P 2 BCh core ( 3Ch ; Ch=S, Se) that possess a P−P bond.…”

Formation of the spirocyclic, Si-centered cage cations [ClP(NSiMe3)2Si(NSiMe3)2P5]+ and [P5(NSiMe3)2Si(NSiMe3)2P5]2+

“…Similar P-N bond ruptures were reported as decomposition pathways of diamino-cyclo-diphosphadiazanes. 26 Intermediate 16 + features a diphosphadiazane [NP] 2 -ring which is assumed to react via a cyclo-reversion reaction to intermediate 17 + . Cation 17 + features an aminoiminophosphane moiety similar to 5 which is tethered to a four-membered SiN 2 P-ring.…”

Trimethylsilyl Pseudohalide Adducts of GaCl3 and B(C6F5)3

“…In recent years, we have frequently used GaCl 3 as Lewis acid for the generation of reactive cations by chloride abstraction [41][42][43][44][45][46][47][48][49] and in GaCl 3assisted [3 + 2] cycloaddition reactions yielding phosphorusnitrogen heterocycles. [50][51][52][53] B(C 6 F 5 ) 3 -adducts have been utilized in our group to stabilize highly labile pseudohalide entities, such as a HCN dimer (Scheme 1A), HN 3 (Scheme 1B) and HNSO (Scheme 1C). [15,16,54] As [Me 3 Si] + can be considered a large proton, [55][56][57] we were interested in synthesizing GaCl 3 and B(C 6 F 5 ) 3 adducts of Me 3 SiÀ X (X = pseudohalogen) to study their structure, connectivity and bonding depending on the used Lewis acid and the pseudohalogen.…”