Diatomic PN – trapped in a cyclo-tetraphosphazene

摘要: (Me3Si)2NPCl2, which is formally capable of eliminating two equivalents Me3SiCl, shown to be a suitable starting material prepare highly reactive PN species by successive elimination Me3SiCl. Me3SiCl can triggered either thermally and/or addition Lewis acid such as GaCl3, thus leading the formation labile aminochlorophosphenium cation in [(Me3Si)2NPCl][GaCl4] and iminophosphenium salt [Me3Si–NP][GaCl4] upon warming ambient temperatures. This work describes synthesis characterization cyclo-tetraphosphazane [PN(dmb)]4 (5) (dmb = 2,3-dimethyl-1,3-butadiene) obtained thermal from (Me3Si)2NPCl2 at 120 °C toluene solution. The intermediate Me3SiNPCl was trapped with dmb form cyclic phosphazane Me3SiN(dmb)PCl, eventually oligomerizes give 5. In presence or chd (chd 1,3-cyclohexadiene) (Me3Si)2NP(OTf)2 reacts Me3SiOTf yield spirocyclic phospholenium salts [Me3SiN(dmb)P(dmb)][OTf] (7) [Me3SiN(chd)P(chd)][OTf] (8), solid state structures were successfully determined. 7 decomposes when exposed moisture an unprecedented ammonium phosphinoxide [P(O)H(dmb)2NH2][OTf] (9). Tetraphosphazane 5 versatile ligand transition metal chemistry. It coordinates η3-fashion {[PN(dmb)]4Mo(CO)3} (5·Mo) able coordinate second fragment, exemplified ditungsten complex{[PN(dmb)]4W2(CO)7} (5·W2) semi-bridging carbonyl ligand. All compounds structurally characterized bonding situation investigated density functional theory natural bond orbital analysis (NBO).