Syntheses and Structure Determinations of Calcium Thiolates

• Published in: Inorganic chemistry Vol. 37; no. 18; pp. 4718 - 4725
• Main Authors: Chadwick, Scott, Englich, Ulrich, Noll, Bruce, Ruhlandt-Senge, Karin
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 07-09-1998
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic980086l

The exploration of synthetic methodologies toward heavy alkaline-earth chalcogenolates resulted in the preparation and structural characterization of a family of calcium thiolates, including [Ca(SC6F5)2(py)4], 1 (py = pyridine), the separated ion-triple [Ca(18-crown-6)(NH3)3)][SMes*]2·2THF, 2 (Mes* = 2,4,6-tBu3C6H2), and the contact triple [Ca(18-crown-6)(SMes*)2]·THF, 3. Compound 1 was prepared by treating [Ca(N(SiMe3)2)2]2 with 4 equiv of HSC6F5 under addition of pyridine. The thiolates 2 and 3 were synthesized by treatment of calcium metal dissolved in dry, liquid NH3 under addition of 2 equiv of HSMes* and crown ether or, alternatively, by the reduction of Mes*SSMes* with calcium metal in dry, liquid ammonia. We also report two reaction products isolated during attempted calcium thiolate syntheses:  [CaBr4(THF)2(μ2-Li)2(THF)4], 4, isolated as the product of a salt elimination reaction between CaBr2 and 2 equiv of [Li(THF) n S-2,4,6- i Pr3C6H2] m . [(NH4)(py)(SC6F5)], 5, was obtained as the sole product in the reaction of metallic calcium with HSC6F5 in liquid ammonia under addition of pyridine. All compounds were characterized by single-crystal X-ray crystallography in addition to IR and NMR spectroscopy.