Arylmino(halogeno)phosphanes XPNC₆H₂tBu₃ (X  Cl, Br, I) and the Iminophosphenium Tetrachloroaluminate [PNC₆H₂tBu₃]^⊕[AlCl₄]^⊖: the First Stable Compound with a PN Triple Bond

Abstract

The cation 4 can be obtained in an amazingly simple raction sequence from phosphorus trichloride 1 and the arylamine 2 via the iminophosphane 3. Spectroscopic findings—δ(31P) = 79.3—and structural data—PNC angle = 177°, PN distance = 147.5 pm—suggest the presence of a triple bond, whereby 4 is isoelectronic with :SiN–aryl.

On the equilibrium between monomeric and dimeric iminochlorophosphanes R–N=P–Cl

“…[5][6][7][15][16][17][18][19] Mes*N= P-Cl and the cation Mes*NP ? was first reported by Niecke et al [20,21].…”

“…For example, Burford et al assumed that dependent upon steric strain in derivatives of [RPNR] 2 the dimer can be destabilized with respect to the monomer [15][16][17][18][19]. The delicate equilibrium is best illustrated by the fact that Mes*N=P-Cl (Mes* = 9, Scheme 3) is observed as an iminochlorophosphane monomer in the solid state [20,21], while slightly smaller substitutents such as 2,6-diisopropylphenyl (6, Scheme 3) or the m-terphenyl (7, Scheme 3) allow dimerization. [5][6][7][15][16][17][18][19] Mes*N= P-Cl and the cation Mes*NP ?…”

Phospha‐Organic Chemistry: Panorama and Perspectives

“…Chemie highly significant results, such as the discoveries of the P¼N, [348] PN, [349] and P¼P bonds [350] and their associated chemistry. Even with such constraints, it is clear that phosphaorganic chemistry has already produced an array of efficient new synthetic tools for building organophosphorus compounds, these tools include well-developed cycloaddition chemistry, several variants of the phospha-Wittig reaction, and some versatile analogues of singlet carbenes.…”

Syntheses, Structure, and Reactivity of Amino(azido)stibanes

“…[8] The stabilities of the monomeric species R-N=E III -X (E = P, As, Sb; X = Cl, OTf) with respect to the corresponding dimers by using Mes* groups (Mes* = 2,4,6-tri-tert-butylphenyl) on N and a chloro or triflate substituent on the pnictogen was only recently studied. [9][10][11] [a] Universität Rostock Institut für Chemie Albert-Einstein-Strasse 3a, 18059 Rostock, Germany E-mail: axel.schulz@uni-rostock.…”