Journal of Fluorine zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA Chemisrty, 66 (1994) 153-158 1.53 Reactions of fluorinated acid anhydrides with metal alkoxides Debyani G. Niyogi, Sukhjinder Singh, Anju Saini and R.D. Verma* Department of Chemistry, Panjab University, Chandigarh-160014 (India) zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGF Abstract Metal alkoxides M(OR), (where M =Ti or Zr and R =methyl or ethyl) have been reacted with trifluoroacetic, trifluoromethanesulfonic and fluorosulfonic anhydrides. The methoxides yielded disubstituted derivatives in all cases, whereas the ethoxides gave different products. In this way new compounds, i.e. Zr(OCH,),(O,CCF,),, Ti(OCH3)2(02CCF,)2, Ti,O(O&CF,),, Zr(OCH3)2(03SCF3)2, Ti(OC2H5)Z(03SCF3)2, Zr(OCH,),(O$F), and Ti(O&H,),(O,SF),, have been isolated in nearly quantitative yield. These reactions also provide an alternative route for the synthesis of previously known compounds Zr(O,CCF,), and Zr(O,SCF,),. The products have been characterised by elemental analysis, infrared and NMR (‘H and “F) spectroscopy and molecular weight deter- mination. Introduction Literature reports regarding trifluoroacetic anhydride, (CF,CO),O PI, and trifluoromethanesulfonic anhy- dride, (CF,SO,),O [2,3], and their reactions with various substrates are widespread. Fluorosulfonic anhydride, (FSO,),O, though known for 40 years has been little investigated [4]. We have recently reported reactions of fluorosulfonic and trifluoromethanesulfonic anhy- drides with titanium(IV) methoxide, Ti(OCH,),, yield- ing products [5, 61 of the type Ti(OCH,),(O,SR),, where R = F or CF,. This further stimulated our interest in the reactions of these fluorinated acid anhydrides and readily available trifluoroacetic anhydride with metal alkoxides, especially methoxides and ethoxides as a means of preparing new mixed ligand derivatives with interesting structural features as well as providing a new route to the preparation of previously known/ unknown completely substituted derivatives. The only known reaction of such type amongst these three an- hydrides is the reaction of caesium trifluoromethoxide with (FSO,),O [7]. Experimental zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA Chemicals Trifluoroacetic anhydride (Aldrich) and trifluoro- methanesulfonic acid (Aldrich) were distilled before use. Trifluoromethanesulfonic and fluorosulfonic an- *Author to whom correspondence should be addressed. hydrides were prepared via literature methods [8, 91 and distilled twice before use. Ti(OCH,), [lo], Ti(OC,H,), [lo], Zr(OCH,), [ll] and Zr(OGH,), [ll] were prepared as described in the literature. Fluoro- sulfonic acid was prepared as described earlier [12]. TiCl, (Fluka) was distilled before use. The solvents were dried and distilled before use. Caution! Fluoro- sulfonic anhydride is a toxic material and should be handled with care 1131. Analy tical Sulfur and fluorine were determined as described earlier [14]. Zirconium and titanium were analysed by standard methods [15]. Carbon and hydrogen were determined microanalytically. Molecular weights were determined cryoscopically in nitrobenzene. All manipulations, i.e. synthetic reactions and sample preparations, were carried out either in a vacuum line or under a dry nitrogen atmosphtre. Instrumentation The IR spectra of the compounds were recorded as neat solids/Nujol/hexachlorobutadiene mulls between AgCl plates on a Perkin-Elmer PE-1430 ratio recording spectrophotometer. The ‘H and 19F NMR spectra were recorded either on a JEOL FX-9OQ or Varian EM- 390 spectrometer operating at 90 MHz, using CFCl, and tetramethylsilane as internal references. Positive chemical shifts are downfield from the reference. 0022-1139/94/%07.00 0 1994 Elsevier Sequoia. All rights reserved SSDI 0022-1139(93)03012-B