Synthesis, Structure, and Thiolysis Reactions of Pyridine Soluble Alkaline Earth and Yttrium Thiolates

A series of alkaline earth thiolates, M(SR)(2) (M = Ca, Sr, Ba), were synthesized from reactions between M(NH(2))(2) and RSH. For R = CMe(3), 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 = CEt(3) were very soluble in pyridine. All the R = SCMe(3) derivatives dissolved in 1-methyl-2-pyrrolidinone (NMP). One yttrium thiolate, ((Et(3)SC)(2)Y(-SCEt(3))Py(2))(2), was also prepared and characterized by single-crystal X-ray diffraction, as was (Sr(-SCEt(3))(2)(NH(3))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: ((Et(3)SC)(2)Y(-SCEt(3))Py(2))(2) P, a = 11.592(1) Å, b = 17.328(2) Å, c = 18.376(2) Å, alpha = 81.617(7) degrees, beta = 79.546(5) degrees, gamma = 78.169(7) degrees, and Z = 2; (Sr(-SCEt(3))(2)(NH(3))Py)(n) P2(1)/c, a = 9.332(2) Å, b = 20.316(2) Å, c = 13.024(1) Å, beta = 102.879(9) degrees, and Z = 4. Solutions of Ca(SCEt(3))(2) and Y(N(SiMe(3))(2))(3) or ((Et(3)SC)(2)Y(-SCEt(3))Py(2))(2) in pyridine were converted to gels or powders, respectively, by reaction with an excess of H(2)S, and the solids were pressed into pellets and thermolyzed to CaY(2)S(4) under flowing H(2)S.