A series of alkaline earth thiolates, M(SR)(2) (M = Ca, Sr, Ba), were synthesized from reactions between M(NH2)(2) and RSH. For R = CMe3, the products were only slightly soluble in pyridine, but the Ca derivative with R = 1-adamantyl was soluble, and the Ca and Sr derivatives with R = CEt3 were very soluble in pyridine. All the R = SCMe3 derivatives dissolved in 1-methyl-2-pyrrolidinone (NMP). One yttrium thiolate, ((Et3SC)(2)Y(mu-SCEt3)Py-2)(2), was also prepared and characterized by single-crystal X-ray diffraction, as was (Sr(mu-SCEt3)(2)(NH3)Py)(n). The former crystallized as discrete dimers with planar (YS)(2) rings, and the latter formed an infinite chain of Sr atoms linked by thiolate bridges. Crystal data : ((Et3SC)(2)Y(mu-SCEt3)PY2)(2) P (1) over bar, a = 11.592(1) Angstrom, b = 17.328(2) Angstrom, c = 18.376(2) Angstrom, beta = 81.617(7)degrees, beta = 79.546(5)degrees, gamma = 78.169(7)degrees, and Z = 2; (Sr(mu-SCEt3)(2)(NH3)Py)(n) P2(1)/c, a = 9.332(2) Angstrom, b = 20.316(2) Angstrom, c = 13.024(1) Angstrom, beta = 102.879(9)degrees, and Z = 4. Solutions of Ca(SCEt3)(2) and Y(N(SiMe3)(2))(3) Or ((Et3SC)(2)Y(mu-SCEt3)PY2)(2) in pyridine were converted to gels or powders, respectively, by reaction with an excess of H2S, and the solids were pressed into pellets and thermolyzed to CaY2S4 under flowing H2S.