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.