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(&mgr;-SCEt(3))Py(2))(2), was also prepared and characterized by single-crystal X-ray diffraction, as was (Sr(&mgr;-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(&mgr;-SCEt(3))Py(2))(2) P&onemacr;, 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(&mgr;-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(&mgr;-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.
Purdy
Andrew P.
AP
Chemistry Division (Codes 6120 and 6170) and Laboratory for the Structure of Matter (Code 6030), Naval Research Laboratory, Washington D.C. 20375.
Berry
Alan D.
AD
George
Clifford F.
CF