Indium Fluoroalkoxide Compounds

Reactions of indium amide complexes with fluorinated alcohols give indium fluoroalkoxide complexes. In[N-t-Bu(SiMe3)]3 reacts with 3 equiv of (CF3)Me2COH to give the homoleptic alkoxide dimer [In{μ-OCMe2(CF3)}{OCMe2(CF3)}2]2, but reactions involving the more acidic alcohols (CF3)2MeCOH and (CF3)2CHOH yield products
containing t-BuNH2, which is derived from the amide ligands. Thus, In[N-t-Bu(SiMe3)]3 reacts with (CF3)2MeCOH to give In[OCMe(CF3)2]3(H2N-t-Bu) and with (CF3)2CHOH to yield In[OCH(CF3)2]3(H2N-t-Bu)3 and
[H3N-t-Bu][In{OCH(CF3)2}4(H2N-t-Bu)]. Reactions of (CF3)2MeCOH and (CF3)2CHOH with In(tmp)3 (tmp =
the anion derived from 2,2,6,6-tetramethylpiperidine) and In(NEt2)3 are less complicated. In(tmp)3 reacts with 3
equiv of (CF3)2CHOH to give In[OCH(CF3)2]3(Htmp) and with 4 equiv of (CF3)2CHOH or (CF3)2MeCOH to
yield the salt compounds [H2tmp][In{OCR(CF3)2}4] (R = H, Me). Trigonal bipyramidal [H2NEt2][In{OCH(CF3)2}4(HNEt2)] and octahedral mer-In[OCMe(CF3)2]3(py)3 are isolated from reactions involving In(NEt2)3. Crystal
structure determinations of [In{μ-OCMe2(CF3)}{OCMe2(CF3)}2]2, [H3N-t-Bu][In{OCH(CF3)2}4(H2N-t-Bu)]·EtOEt,
In[OCH(CF3)2]3(Htmp), [H2tmp][In{OCMe(CF3)2}4], In[OCMe(CF3)2]3(py)3, and [H2NEt2][In{OCH(CF3)2}4(HNEt2)] were carried out.