Selenide and selenolate compounds of indium: a comparative study of In–Se bond-forming reactions

Abstract

A range of In–Se bond-forming reactions have been investigated, including insertion of selenium into either an In–C or In–S bond, reaction of an indium halide with a magnesium selenolate and via chlorosilane elimination. The reaction of InBu ^t ₃ with Se yielded [Bu ^t ₂ In(µ-SeBu ^t )] ₂ and [Bu ^t In(µ ₃ -Se)] ₄ . In contrast, In(CMe ₂ Et) ₃ and InBu ⁿ ₃ with Se preferentially formed [(Me ₂ EtC)In(µ ₃ -Se)] ₄ and [Bu ⁿ In(µ ₃ -Se)] ₄ , respectively. The reaction of In(CMe ₂ Et) ₃ with Te yielded [(Me ₂ EtC)In(µ ₃ -Te)] ₄ ]. The compound [Bu ^t In(µ ₃ -Se)] ₄ is also formed from the reaction of [Bu ^t ₂ In(µ-SBu ^t )] ₂ with either Se or SePPh ₃ , while both it and [Bu ^t In(µ-SeBu ^t )] ₂ may be prepared from [Bu ^t ₂ In(µ-Cl)] _n and (Bu ^t Se)MgCl. Similarly, [Bu ⁿ ₂ In(µ-SeBu ^t )] ₂ may be prepared from [Bu ⁿ ₂ In(µ-Cl)] ₂ . However, the reaction of [(Me ₂ EtC) ₂ In(µ-Cl)] ₂ with (Bu ^t E)MgCl (E = S, Se or Te) yielded [(Me ₂ EtC)In(µ ₃ -E) ₄ ]. Reaction of [Bu ^t ₂ M(µ-Cl)] _n (M = In or Ga) with Se(SiMe ₃ ) ₂ yielded the silylselenolate compounds [Bu ^t ₂ M(µ-SeSiMe ₃ )] ₂ . The various In–Se bond-forming reactions are compared. The molecular structures of [Bu ^t ₂ In(µ-EBu ^t )] ₂ (E = S or Se) have been determined by X-ray crystallography.