1309766-99-1Relevant articles and documents
Synthesis of blue imino(pentafluorophenyl)phosphane
Kuprat, Marcus,Lehmann, Mathias,Schulz, Axel,Villinger, Alexander
experimental part, p. 5784 - 5792 (2011/08/05)
The reaction of AgC6F5 with monomeric iminophosphanes of Mes*-N=P-X (X = Cl, I) in CH2Cl2 at ambient temperature gives imino(pentafluorophenyl)phosphane, Mes*N=P(C 6F5) (1), in almost quantitative yield (96%), which could be isolated as a highly viscous blue oil. The same reaction with LiC 6F5 results in the formation of imino(amino)phosphane (C6F5)2P-N(Mes*)-P=NMes* (2) (yield 93%). In the second series of experiments the analogous reaction of MC 6F5 (M = Ag, Li) with dimeric [Cl-P(μ-N-Dipp)] 2 was studied, leading to the formation of [R-P(μ-N-Dipp)] 2 (R = C6F5) (3) for M = Ag, while only decomposition products such as P(C6F5)3 were observed in the reaction with the Li salt. Highly labile Mes*-N=P-C 6F5 (1) decomposes at ambient temperatures, forming among other products the diphosphane (C6F5)2P- P(C6F5)2 (4). Reaction of 1 with Fe 2(CO)9 yields the iron carbonyl complexes Mes*-N=P(C6F5)?Fe(CO)4 (5) and [Mes*-N=P(C6F5)]2?Fe(CO) 3 (6). The structure, bonding, and potential energy surface are discussed on the basis of B3LYP/6-31G(d,p) computations. According to time-dependent B3LYP calculations, the blue color of 1 arises from an n → π* electronic transition.
