Metallocene and Organo-main Group Trifluoromethanesulfonates

Abstract

The substituted metallocene compounds Cp 2 M(OSO 2 CF 3 ) 2 (Cp=g 5 -C 5 H 5 ; M = Ti, Zr, Hf, Nb, Mo), CpTi(O-SO 2 CF 3 ) 3 AE 0.75(1,2-dimethoxyethane), and the organo-main group compounds (C 6 H 5 ) 3 M¢(OSO 2 CF 3 ) (M¢=Si, Ge), (C 6 H 5 ) 2 Sn(OSO 2 CF 3 ) 2 and (C 6 H 5 ) 3 Sb(OSO 2 CF 3 ) 2 , were synthesized from the corresponding chloride or bromide compounds and silver trifluoromethanesulfonate (triflate) and characterized spectroscopically, including a detailed analysis of their IR spectra. Triflate coordination is typically monodentate, but CpTi(OSO 2 CF 3 ) 3 AE 0.75(1,2-dimethoxyethane) and the organo-germanium triflate show evidence of bidentate CF 3 SO À 3 ligands and are likely to have polymeric structures. Conductance measurements in nitromethane, acetone and acetonitrile have demonstrated the ease of triflate substitution, with a limited kinetic study of acetone solvation of the Ti and Hf compounds supporting an associative pathway. Three new catalysts for the polymerization of tetrahydrofuran, Cp 2 HfCl 2 / Ag(OSO 2 CF 3 ), CpTiCl 3 /Ag(OSO 2 CF 3 ) and (C 6 H 5 ) 2 SiCl 2 /Ag(OSO 2 CF 3 ), are also reported.

Space-confined indicator displacement assay inside a metal–organic framework for fluorescence turn-on sensing

“…S1†) and 1 H NMR spectra of the solutions obtained by digesting the solids in HF (aq.)/d6-DMSO. The success of N-alkylation is indicated by the appearance of the characteristic IR bands of the ethylene group (3086 cm –1 ) and the triflate counteranion (1280, 1255, 1170 and 1030 cm –1 ) 16. Anion exchange is indicated by the appearance of new multiple bands in the ranges of 1245–1160, 1090–1010, and 850–840 cm –1 , which also appear in the spectra of NaPsO.…”

Synthesis and Structure of an Extremely Air‐Stable Binuclear Hafnocene Perfluorooctanesulfonate Complex and Its Use in Lewis Acid‐Catalyzed Reactions

“…For example, Angus-Dunne reported the incorporation of a triflate ion as the counteranion to [Cp 2 HfCl 2 ] for the generation of hafnocene bisA C H T U N G T R E N N U N G (triflate) (3), which was employed in the polymeri-zation of THF. [6] Unfortunately, the compound was extremely unstable in air due to facile hydrolysis. From the standpoint of the practical utilization of cationic hafnocene derivatives as catalysts, it is highly desirable to lower the hygroscopic character while improving the Lewis acidity of the substance.…”

“…The dilemma is that with an increase in acidity, the compound becomes more susceptible to hydrolysis. For example, Angus‐Dunne reported the incorporation of a triflate ion as the counteranion to [Cp 2 HfCl 2 ] for the generation of hafnocene bis(triflate) ( 3 ), which was employed in the polymerization of THF 6. Unfortunately, the compound was extremely unstable in air due to facile hydrolysis.…”

(N,Se) and (Se,N,Se) Ligands Based on Carborane and Pyridine Fragments – Reactivity of 2,6‐[(1′‐Me‐1′,2′‐closo‐C2B10H10)SeCH2]2C5H3N towards Copper and Silver

“…[21e], The ionic nature of 4 is suggested by the presence of four nonsplit bands at ν̃ = 1277, 1235, 1156, and 1024 cm –1 , which are assigned to ν asym (SO 3 ), ν asym (CF 3 ), ν sym (CF 3 ), and ν sym (SO 3 ) stretching vibrations, respectively, as also observed for the ionic AgOTf. [23a] For 3 , the splitting of the band corresponding to ν asym (SO 3 ) into two components (ν̃ = 1284, 1260 cm –1 ) indicates a covalently bonded OTf ligand. In addition, a band at ν̃ = 392 cm –1 in the IR spectrum of 3 was assigned to the ν(N–Ag) mode.…”