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(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)2Y(μ-SCEt3)Py2)2, was also prepared and characterized by
single-crystal X-ray diffraction, as was
(Sr(μ-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)2Y(μ-SCEt3)Py2)2
P1̄, a = 11.592(1) Å, b =
17.328(2)
Å, c = 18.376(2) Å, α = 81.617(7)°, β
= 79.546(5)°, γ = 78.169(7)°, and Z =
2;
(Sr(μ-SCEt3)2(NH3)Py)n
P21/c,
a = 9.332(2) Å, b = 20.316(2) Å,
c = 13.024(1) Å, β = 102.879(9)°, and
Z = 4. Solutions of
Ca(SCEt3)2 and
Y(N(SiMe3)2)3 or
((Et3SC)2Y(μ-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.