On 1,3-phosphaazaallenes and their diverse reactivity

Abstract

1,3-Phosphaazaallenes are heteroallenes of the type RP=C=NR’ and little is known about their reactivity. In here we describe the straightforward synthesis of ArPCNR (Ar = Mes*, 2,4,6-tBu-C6H2; MesTer, 2,6-(2,4,6-Me3C6H2)-C6H3; DipTer, 2,6-(2,6-iPr2C6H2)-C6H3; R...

Cyano(triphenylsilyl)phosphanide as a Building Block for P,C,N Conjugated Molecules

“… [17] Deprotonation of aryl cyanophosphines gives cyanophosphides but only sterically protected species such as I (Scheme 1 ) are stable while smaller derivatives eliminate cyanide salts. [18] …”

“…Similar observations have been reported with anions of the type [Ar‐PCN] − . [18] Nevertheless single crystals of [Na(18‐C‐6)][ 2 ] and [Na(18‐C‐6)][ 3 ] were grown at low temperatures by layering a solution of [Na(18‐C‐6)][N(SiMe 3 ) 2 ] with a solution of Ph 3 E‐PCO. The structures of all compounds [Na(18‐C‐6)][ 1 – 3 ] were determined by X‐ray diffraction (XRD) experiments (see the SI for details).…”

On the ambiphilic character of phosphanylidenephosphoranes and manipulation of phosphinidenoid reactivity with Lewis acids

“…[18,[24][25][26][27] This phosphinidenoid-type reactivity was revisited by our group and we could convincingly demonstrate that PMe3 can readily be liberated upon addition of a stronger Lewis-base. For instance, an N-heterocyclic carbene (NHC), N-heterocyclic olefin (NHO) or isocyanate for PMe3 exchange yielded NHC phosphinidene adducts, [21] C(sp 2 )-H activated P-substituted NHOs [21] or 1,3phosphaazaallenes, [28] respectively. The latter were shown to be facile precursors for cyanophosphines.…”

Cyano(triphenylsilyl)phosphanide as a Building Block for P,C,N Conjugated Molecules

“…[17] Deprotonation of aryl cyanophosphines gives cyanophosphides but only sterically protected species such as I (Scheme 1) are stable while smaller derivatives eliminate cyanide salts. [18] The phosphorus analogue of the cyanamide dianion, [PCN] 2À , was studied theoretically. [19] Recently, compounds were discovered which can be viewed as synthons for [PCN] 2À .…”

“…Similar observations have been reported with anions of the type [Ar-PCN] À . [18] Nevertheless single crystals of [Na(18-C-6)][2] and [Na(18-C-6)][3] were grown at low temperatures by layering a solution of [Na(18-C-6)][N(SiMe 3 ) 2 ] with a solution of Ph 3 E-PCO. The structures of all compounds [Na(18-C-6)][1-3] were determined by X-ray diffraction (XRD) experiments (see the SI for details).…”