Indium Fluoroalkoxide Compounds

Abstract

Reactions of indium amide complexes with fluorinated alcohols give indium fluoroalkoxide complexes. In[N-t-Bu(SiMe(3))](3) reacts with 3 equiv of (CF(3))Me(2)COH to give the homoleptic alkoxide dimer [In{&mgr;-OCMe(2)(CF(3))}{OCMe(2)(CF(3))}(2)](2), but reactions involving the more acidic alcohols (CF(3))(2)MeCOH and (CF(3))(2)CHOH yield products containing t-BuNH(2), which is derived from the amide ligands. Thus, In[N-t-Bu(SiMe(3))](3) reacts with (CF(3))(2)MeCOH to give In[OCMe(CF(3))(2)](3)(H(2)N-t-Bu) and with (CF(3))(2)CHOH to yield In[OCH(CF(3))(2)](3)(H(2)N-t-Bu)(3) and [H(3)N-t-Bu][In{OCH(CF(3))(2)}(4)(H(2)N-t-Bu)]. Reactions of (CF(3))(2)MeCOH and (CF(3))(2)CHOH with In(tmp)(3) (tmp = the anion derived from 2,2,6,6-tetramethylpiperidine) and In(NEt(2))(3) are less complicated. In(tmp)(3) reacts with 3 equiv of (CF(3))(2)CHOH to give In[OCH(CF(3))(2)](3)(Htmp) and with 4 equiv of (CF(3))(2)CHOH or (CF(3))(2)MeCOH to yield the salt compounds [H(2)tmp][In{OCR(CF(3))(2)}(4)] (R = H, Me). Trigonal bipyramidal [H(2)NEt(2)][In{OCH(CF(3))(2)}(4)(HNEt(2))] and octahedral mer-In[OCMe(CF(3))(2)](3)(py)(3) are isolated from reactions involving In(NEt(2))(3). Crystal structure determinations of [In{&mgr;-OCMe(2)(CF(3))}{OCMe(2)(CF(3))}(2)](2), [H(3)N-t-Bu][In{OCH(CF(3))(2)}(4)(H(2)N-t-Bu)].EtOEt, In[OCH(CF(3))(2)](3)(Htmp), [H(2)tmp][In{OCMe(CF(3))(2)}(4)], In[OCMe(CF(3))(2)](3)(py)(3), and [H(2)NEt(2)][In{OCH(CF(3))(2)}(4)(HNEt(2))] were carried out.

The Facile Preparation of Weakly Coordinating Anions: Structure and Characterisation of Silverpolyfluoroalkoxyaluminates AgAl(ORF)4, Calculation of the Alkoxide Ion Affinity

“…This parallels recent observations made for the homologous compound In(hftb) 3 (HFTB OC(CH 3 )(CF 3 ) 2 ), which is only isolable as a donor adduct and can coordinate up to three additional pyridine ligands. [19] To avoid the use of the coordinating solvent (OEt 2 ), one equivalent of AlMe 3 in heptane was added to HOÀC(H)(CF 3 ) 2 (3 equiv) in toluene at 60 8C [Eq. (1 a)], but this only gave an intensely red-violet solution.…”

Synthesis and Characterization of Five‐Coordinate Gallium and Indium Complexes Stabilized by Tridentate, Substituted Pyrrole Ligands

“…1 H and 13 C NMR spectra were recorded with a Bruker AC 200 spectrometer. Chemical shifts for 1 H and 13 C spectra were recorded in ppm relative to the residual protons of the solvent or the 13 (20 mL) with stirring at Ϫ78°C.…”

“…Chemical shifts for 1 H and 13 C spectra were recorded in ppm relative to the residual protons of the solvent or the 13 (20 mL) with stirring at Ϫ78°C. The mixture was allowed to warm to room temperature and stirred for 5 h. The resultant suspension was filtered through Celite.…”

“…1 H NMR (CDCl 3 ): δ ϭ Ϫ0.37 (s, 6 H, GaMe), 2.29 (s, 12 H, NMe 2 ), 3.48 (s, 4 H, CH 2 N), 5.89 (s, 2 H) ppm. 13 A small amount of complex 2 was present in 6 (less than 3% by 1 H NMR spectroscopy), which prevented a reasonable elemental analysis from being obtained.…”

Synthesis and structural characterisation of gallium and indium fluoroalkoxide ‘ate’ complexes

“…On seeking to explore the related synthetic chemistry of the fluoroalkoxides of gallium and indium, a salt elimination approach was adopted as this had previously been reported to be successful in the synthesis of fluorinated and non-fluorinated alkoxides; Al(OCH(CF 3 ) 2 ) 3 was synthesised from AlCl 3 and Na(OCH(CF 3 ) 2 ) using reflux conditions and an excess of hexafluoroisopropanol [12] while a series of In(OR) 3 compounds have been prepared from the reactions of Gp 13 metal halides with non-fluorinated alkali metal alkoxides [13][14][15]. Another alternative route to indium fluoroalkoxides using an amide-alcohol exchange route has been exploited by Hoffman and co-workers [16][17][18][19][20][21], however, Carmalt and co-workers have recently described problems of halide incorporation in gallium alkoxides founded on incomplete amide formation from GaCl 3 [22].…”