The first compound with an unusual type of anion, [Li(SR)₂]^–: bis(μ₂-aqua-d₂)tetrakis(aqua-d₂)dilithium(I) bis[bis(tri-tert-butoxysilanethiolato-κ²O,S)lithate(I)] dihydrate-d₂

Abstract

The title complex, [Li2(D2O)6][Li(C9H27SSiO3)2]2.2D2O, is the first compound with an S-M bond (M = alkali metal) within an unusual type of lithate anion, [Li(SR)2]- {where R is Si[OC(CH3)3]3}. There is a centre of symmetry located in the middle of the Li2O2 ring of the cation. All Li atoms are four-coordinate, with LiO4 (cations) and LiO2S2 (anions) cores. The singly charged [Li(SR)2]- anions are well separated from the doubly charged [Li2(D2O)6]2+ cations; the distance between Li atoms from differently charged ions is greater than 5 A. Both ion types are held within an extended network of O-D...O and O-D...S hydrogen bonds.

A 32 vertex polyhedron via supramolecular assembly of silanedithiolate silanolate units

“…The Si-S distances 2.1104(11) and 2.1173(11) A ˚in the four crystallographically independent molecules are significantly longer than in the two other structurally characterized lithium silanolates in which Si-S bond distances range from 2.051(2) to 2.079(1) A ˚. 24,[42][43][44] This increase in Si-O/S bond length can also be interpreted in terms of a smaller contribution of ps* interactions owing to the presence of multiple chalcogen atoms at a single silicon site. In agreement with that, the silicon-oxygen bonds (1.612(2) and 1.617(2) A ˚) are longer than for comparable lithium silanolates (shortest Si-O: 1.584, longest: 1.616, mean value 1.606 A ˚).…”

“…It should be mentioned that even simple lithium silanethiolates have been structurally characterized for only two other substituents. [42][43][44] In 4 however, further functionalities are available for coordination besides the silanethiolate unit. In fact, 4 represents the first silanedithiolate silanolate complex so far and we anticipate that the presence of soft (S) and hard (O) donor sites in close proximity may furnish some unusual coordination behavior which we would like to explore in the future.…”

A study of chirality in bis(1,2-dimethoxyethane-κ2O,O′)sodium bis(tri-tert-butoxysilanethiolato-κ2O,S)sodate

“…Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity typical for sodium silanethiolates (c.f. Kloskowska et al, 2006b). Nevertheless, asymmetry of the silanethiolate ligand also seems to be important in the manner described below.…”

“…This observation suggests that the coordination and hydrogen-bond formation capabilities of the solvent are strong structureforming factors, which is not surprising. It is noteworthy that both SSi(O t Bu) 3 groups are of the same chirality in the anionic fragment (Kloskowska et al, 2006b).…”

Intramolecular Interactions in Crystals of Tris(2,6-diisopropylphenoxy)silanethiol and Its Sodium Salts

“…Systematic studies undertaken to analyze the influence of metal, ligand, and solvent on the structure of thiolates of group 1 elements were reviewed . Because of the well recognized ability of thiolato ligands to form bridges between metal ions, alkali metal thiolates exhibit the varying extent of aggregation; they crystallize as rare, mononuclear species, common, four-membered M 2 S 2 rings, ,, ladders, ,, cubanes, ,, or other coordination oligomers and polymers. ,,,, The aggregation can be prevented by the increase of the steric hindrance of thiolato ligand ,,, and/or addition of coligands such as tetrahydrofuran ,,, or N , N , N ′, N ′-tetramethylethylenediamine. ,,,, It is possible to obtain crystalline compounds with separate or contact thiolato anions and alkali metal cations surrounded either by water or crown ethers. ,,, Quite unusual ion pairs of different character, 2Li­(TBST) 2 – Li 2 (D 2 O) 6 2+ and Na­(TBST) 2 – Na­(DME) 2 + , were structurally characterized by the researchers from our department. Introduction of other functional groups into the molecule of thiol greatly influences the structure of the resulting alkali metal thiolate (e.g., ref ), but this research is not reviewed in detail here.…”