Indium Tris(alkylthiolate) Compounds

In[N-t-Bu(SiMe3)]3 reacts with RSH to give In(SR)3 (R = t-Bu, i-Pr). The tert-butyl derivative is formulated as
the dimer [In(S-t-Bu)2(μ-S-t-Bu)]2 on the basis of NMR data, molecular weight determination, and its solubility.
The limited solubility of the isopropylthiolate complex suggests that it is a polymer. [In(S-t-Bu)2(μ-S-t-Bu)]2
and [In(S-i-Pr)3]n react with pyridine and p-Me2Npy, respectively, to form In(S-t-Bu)3(py) and In(S-i-Pr)3(p-Me2Npy)2, which were characterized by X-ray crystallography. In(S-t-Bu)3(py) is trigonal pyramidal, and In(S-i-Pr)3(p-Me2Npy)2 is trigonal bipyramidal. In both structures the pyridine ligands occupy the apical positions.
Crystal data are as follows:  C17H32InNS3 at 223 K:  P21/c (monoclinic), a = 10.1490(5) Å, b = 24.3811(13) Å,
c = 18.8484(10) Å, β = 104.8100(10)°, and Z = 8; C23H41N4S3In·CH2Cl2 at 223 K:  P1̄ (triclinic), a =
10.620(1) Å, b = 11.568(1) Å, c = 14.892(2) Å, α = 79.54(1)°, β = 75.88(1)°, γ = 66.08(1)°, and Z = 2.