The formation of [Ir(CO)Cl2(PEt3)2(NF2)] and its rhodium analogue: complexes containing the novel difluoroamido ligand
作者:Russell W. Cockman、E. A. V. Ebsworth、John H. Holloway
DOI:10.1039/c39860001622
日期:——
Chlorodifluoroamine reacts at 190 K in CH2Cl2 with [M(CO)Cl(PEt3)2](M = Ir or Rh) to give [M(CO)Cl2(PEt3)2(NF2)], characterised by 19F and 31 P n.m.r. spectroscopy (the 15N derivative was also obtained for M = Ir); the novelcomplexes decompose in solution at temperatures above 240 K, the products of decomposition including N2F4.
rates (20, 50 and 100 standard cc min−1). From a direct reaction, NF2Cl and NFCl2 gases were obtained as products. With high NF2Cl and NFCl2 selectivity for N2, such as higher than 90% selectivity as the nitrogen containing molecule base at temperatures below 298 K, an n value of around 2.2–2.3 was obtained. The selectivity of NF2Cl and NFCl2 decreased to less than 70% at temperatures higher than 318 K
NH之间的反应4 F / Ñ HF和气态的ClF 3在各种在280-320的K的温度下进行了检查ñ -值(Ñ 在该NH = 2.2,2.3,2.4,2.7,2.8,3.0,3.1和4.0)4 F / n HF是一种熔融盐,具有三种ClF 3气体流速(20、50和100标准cc min -1)。通过直接反应,获得了作为产物的NF 2 Cl和NFCl 2气体。NF 2 Cl和NFCl 2对N 2的选择性高例如,在低于298 K的温度下,作为含氮分子碱的选择性高于90%时,n值约为2.2–2.3。在高于318 K的温度下,由于N 2副产物的量增加,NF 2 Cl和NFCl 2的选择性降至70%以下。通过以[NH 3 ClF 2 ] +(FH)n F-作为中间体形成的反应机理,可以得到高选择性的NF 2 Cl和NFCl 2。