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)(mu-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)(mu-S-t-Bu)](2) and [Ln(S-i-Pr)(3)](n) react with pyridine and p-Me(2)Npy, respectively, to form In(S-t-Bu)(3)(py) and In(S-i-Pr)(3)(p-Me-2-Npy)(2), which were characterized by X-ray crystallography. In(S-t-Bu)(3)(py) is trigonal pyramidal, and In(S-i-Pr)(3)(p-Me(2)Npy)(2) is trigonal bipyramidal. In both structures the pyridine ligands occupy the apical positions. Crystal data are as follows : C17H32InNS3 at 223 K : P2(1)/c (monoclinic), a = 10.1490(5) Angstrom, b = 24.3811(13) Angstrom, 18.8484(10) Angstrom, beta = 104.8100(10)degrees, and Z = 8; C23H41N4S3In . CH2Cl2 at 223 K: : P (1) over bar (triclinic), a =10.620(1) Angstrom, b = 11.568(1) Angstrom, c = 14.8926(2) Angstrom, alpha = 79.54(1)degrees, beta = 75.88(1)degrees, gamma = 66.08(1)degrees,and Z =2.