首页 | 本学科首页   官方微博 | 高级检索  
     检索      


Stable CI3+ salts and attempts to prepare CHI2+ and CH2I+
Authors:Raabe Ines  Himmel Daniel  Müller Sonja  Trapp Nils  Kaupp Martin  Krossing Ingo
Institution:Albert-Ludwigs-Universit?t Freiburg, Institut für Anorganische und Analytische Chemie, Albertstr. 21, D-79104, Freiburg i. Br., Germany.
Abstract:The room-temperature stable CI3+ salts CI3+pftb](-)1 and CI3]+al-f-al](-) 2(pftb](-) = Al(OC(CF3)3)4](-); al-f-al](-) = ((CF3)3CO)3Al-F-Al(OC(CF3)3)3](-)) were prepared in quantitative yields from purified CI4 and the corresponding silver aluminates with total exclusion of light (NMR, IR, UV-VIS, X-ray diffraction). The isolated CI(3)(+) cation is trigonal planar with a sum of <(I-C-I) = 360.0 degrees (1) and 359.9 degrees (2). Attempts to prepare CHI2+ and CH2I+ salts from CHI3 or CH2I2/Agpftb] mixtures remained unsuccessful; the reaction with CH2I2 leads to the formation of the adduct Ag(CH2I2)3]+pftb](-)3, while for HCI3, dismutation with formation of 1 as well as 3 was observed. All particles were also calculated at the MP2/TZVPP level to predict the vibrational and electronic spectra as well as to calculate the Gibbs free energies of all reactions (DeltaG degrees , gas phase and CH2Cl2 solution). Quantum chemical calculations were also used to investigate the stability of the pftb](-) anion against the electrophilic attack of the CX3+ and CHnX3-n+ cations (X = F-I, n = 1-3). The strength of the Lewis acidity of these cations and of the isoelectronic boron halides BX()and BHnX3-n have been established on the basis of their fluoride ion affinities (FIAs). The FIAs of the carbon and the boron containing compounds show opposite trends, with fluorinated halomethyl cations being stronger acids than their heavier congeners but iodinated holoboranes being stronger acids than their lighter homologues.
Keywords:
本文献已被 PubMed 等数据库收录!
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号