Syntheses and Structure Determinations of Calcium Thiolates

Abstract

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(SC(6)F(5))(2)(py)(4)], 1 (py = pyridine), the separated ion-triple [Ca(18-crown-6)(NH(3))(3))][SMes](2).2THF, 2 (Mes = 2,4,6-tBu(3)C(6)H(2)), and the contact triple [Ca(18-crown-6)(SMes)(2)].THF, 3. Compound 1 was prepared by treating [Ca(N(SiMe(3))(2))(2)](2) with 4 equiv of HSC(6)F(5) under addition of pyridine. The thiolates 2 and 3 were synthesized by treatment of calcium metal dissolved in dry, liquid NH(3) under addition of 2 equiv of HSMes and crown ether or, alternatively, by the reduction of MesSSMes with calcium metal in dry, liquid ammonia. We also report two reaction products isolated during attempted calcium thiolate syntheses: [CaBr(4)(THF)(2)(&mgr;(2)-Li)(2)(THF)(4)], 4, isolated as the product of a salt elimination reaction between CaBr(2) and 2 equiv of [Li(THF)(n)()S-2,4,6-(i)()Pr(3)C(6)H(2)](m)(). [(NH(4))(py)(SC(6)F(5))], 5, was obtained as the sole product in the reaction of metallic calcium with HSC(6)F(5) in liquid ammonia under addition of pyridine. All compounds were characterized by single-crystal X-ray crystallography in addition to IR and NMR spectroscopy.

Charge-assisted N(+)–H···(−)S hydrogen bonds in the crystal structure of selected diammonium thiophenolates

“…9a) strengthened by C-HÁÁÁp interactions (Table 2) different from the 3-D network of crystal 2. The NÁÁÁS distances in three salts lie in the range 3.155 (3)-3.286 (3) Å , comparable with values observed in other silanethiolates [26,27], aromatic thiolate [25,39,40], ditiocarbamates [41][42][43] or sulfides [44][45][46].…”

[Be(ND3)4]Cl2: Synthesis, Characterisation and Space‐Group Determination Guided by Solid‐State Quantum Chemical Calculations

“…Additionally, two chloride anions are present with Be-Cl distances of more than 3.75 Å. The Be-N bond lengths of the [Be(ND 3 [12] for [Be(iPr-N=C=N-iPr) 4 ] 2+ at 1.734(6) Å, [13] for [Be(Me-Im) 4 ] 2+ (Me-Im = Nmethylimidazole) at 1.703(3) Å, [14] for [Be(SPh) 2 (py)(NH 3 )] 2 -(18-crown-6) at 1.724(4) and 1.731(4) Å, [15,16] and [Be(NH 3 ) 4 ] 2+ at 1.725(1)-1.733(3) Å. [8] The N-Be-N angles observed are close to the tetrahedral ones and are between 106.9 (10) (1) and 109.6(1)°.…”

Deprotonation of μ3‐Methylidyne Groups on a Ti3O3 Support: A Way to Build Oxotitanocubanes Containing Alkali and Alkaline‐Earth Metals

“…The MϪO bond lengths in the magnesium and strontium derivatives are in the expected ranges for oxocomplexes with high numbers of oxygen atoms. [14] The TiϪC(1) bond lengths decrease from magnesium to strontium [Mg ϭ 2.020(10) Å av., Ca ϭ 1.990(7) Å av., Sr ϭ 1.970(2) Å av. ], consistent with the higher steric requirement of the metal center.…”