Synthesis and Characterization of the Monomeric Three-Coordinate Indium Thiolate and Selenolate Complexes In[E(2,4,6-t-Bu₃C₆H₂)]₃ (E = S, Se)

The synthesis and characterization of the monomeric neutral three-coordinate indium thiolate and selenolate derivatives In[S(2,4,6-t-Bu₃C₆H₂)]₃ (1) and In[Se(2,4,6-t-Bu₃C₆H₂)]₃·2PhMe (2) are described. Compound 1 was synthesized by the reaction of In[N(SiMe₃)₂]₃ with 3 equiv of HS(2,4,6-t-Bu₃C₆H₂) in toluene whereas 2 was obtained by the reaction of InEt₃ with 3 equiv of HSe(2,4,6-t-Bu₃C₆H₂) in the same solvent. The compounds display an essentially planar trigonal coordination at the indium atom with an average In-S bond length of 2.398(6) Å and an average In-Se distance of 2.505(3) Å. The compounds were characterized by IR and ¹H NMR (⁷⁷Se NMR in the case of 2) spectroscopy and by X-ray crystallography. Crystal data with Mo Kα (λ = 0.710 69 Å) at 130 K: 1, a = 10.244(3) Å, b = 26.31(2) Å, c = 20.070(10) Å, β = 90.74°, V = 5409(5) ų, Z = 4, space group P2₁/n, 4834 (I > 2.5σ(I)) data, R = 0.061; 2, a = 14.538(4) Å, b = 14.796(3) Å, c = 16.701(5) Å, α = 85.65(2)°, β = 83.60(2)°, γ = 61.64(2)°, V = 3140.4(13) ų, Z = 2, space group P1̄, 8415 (I > 3σ(I)) data, R = 0.049.