Crown Ether Complexes of Alkali‐Metal Chlorides from SO₂

Abstract

The structures of alkali-metal chloride SO solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) ]Cl⋅4 SO (3) and [M(12-crown-4) (SO )]Cl⋅4 SO (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO -solvated alkali-metal chlorides [MCl⋅3 SO ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO at ambient temperature was revealed by IR spectroscopy of the neat compounds.

New Group 14 Element Substituted Phosphaalkenes

“…As far as we know, no phosphorus substituted tetrasilaether have been reported until now. Known in the literature are only cyclic molecules with a {SiMe 2 SiMe 2 } 2 O bridge, for example in organic/inorganic crown ethers and some complexes of alkaline (earth) metal salts, which were presented by our group over the last years . Also known are cyclic compounds like [OSiMe 2 SiMe 2 ] 2 , which represents the silicon analogue to 1,4‐dioxane , …”

Chalcogen Bonding of SO2 and s‐Block Metal Iodides Near Room Temperature: A Remarkable Structural Diversity

“…Sulfur dioxide can be used in a large variety of reactions which allow functionalization due to SO 2 inser-tive iodide salt and respective crown-ether in SO 2 solution. Two-dimensional networks were obtained within the alkaline earth metal compounds [Mg( [12] (11). The iodosulfite ion ISO 2 was obtained either by shielding Na + ions with [12]crown-4, conversion of MgI 2 with [15]crown-5, conversion of CaI 2 with [18]crown-6 or conversion of BaI 2 with [18]crown-6 (11, as aforementioned).…”

Alkaline Earth Metal Template (Cross‐)Coupling Reactions with Hybrid Disila‐Crown Ether Analogues

“…In the case of the early alkaline earth‐metal ions, even the commercially available cyclosiloxanes are able to dissolve salts characterized by a high lattice energy and stable complexes were obtained . Soft cations like Rb + and Cs + so far relucted silyl ether coordination . Overall, sila‐ligands are suitable ligands for early s‐block‐metal coordination chemistry and opened a new chapter in host–guest chemistry over the years.…”

“…[32] Soft cations like Rb + + and Cs + + so far relucteds ilyl ether coordination. [33,34] Overall,s ila-ligands are suitable ligands fore arly s-block-metal coordination chemistry and opened an ew chapter in hostguest chemistry over the years. In this contribution, we report the synthesis of novel hybrid disila-crown ether moieties, which are accessible by alkaline earth metal-template synthesis.…”