Aryl(dimethylaminomethyl)phosphinic Acid Esters: Syntheses, Structures, and Reactions with Halogen Hydrogen Acids, Tin Halides, and Trimethyl Halosilanes

作者：Lutter Michael^*; Jurkschat Klaus

来源：European Journal of Inorganic Chemistry, 2018, 2018(30): 3481-3490.

DOI：10.1002/ejic.201800343

• Phosphorus
• Tin
• Silicon
• X-ray diffraction
• Hydrogen bridges

This paper reports the synthesis of the aryl(iodomethyl)phosphinic acid ethyl esters, Ar(ICH2)P(O)OEt (Ar = Ph, Ar = mesityl), which, via dimethyamination, are converted to the corresponding aryl(dimethylaminomethyl)phosphinic acid ethyl esters, Ar(Me2NCH2)P(O)OEt (Ar = Ph, Ar = mesityl). Upon reaction with hydrogen chloride, compound Me2NCH2(Ph)P(O)OEt forms its hydrochloride salt as a crystalline material. Depending on the reaction conditions, treatment of Me2NCH2(Ph)P(O)OEt with SnCl2 gave either [Me2HNCH2(Ph)P(O)OEt][SnCl3] or the mixed-valent dinuclear tin salt [{Me2HNCH2(Ph)P(O)O}(4)SnCl2][SnCl3](2), as its dichloromethane solvate. The reaction of Me2NCH2(Mes)P(O)OEt with SiMe3I gives the diorgano bis(trimethylsiloxy)phosphinium iodide [Me2NCH2(Mes)P(OSiMe3)(2)]I, as its toluene solvate. In solution, it is involved in an equilibrium with Me2NCH2(Mes)P(O)OSiMe3 and SiMe3I. From the hydrolysis of [Me2NCH2(Mes)P(OSiMe3)(2)]I, the hydrogen iodide derivative [Me2HNCH2(Mes)P(O)OH]I was obtained as three different solvates. [Me2NCH2(Mes)P(OSiMe3)(2)]I reacted with SnF2 to give a product mixture from which the mixed-valent tin compound [{(Sn2Me2NCH2)-Me-II(Mes)P(O)(2)}(4)(SnF2)-F-IV]I-2, was isolated. The compounds were characterized by NMR and IR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction analysis.

• 出版日期2018-8-15