Silver complexes stabilized by large silanethiolate ligands - crystal structures and luminescence properties.

Bulky silanethiolate and disiladithiolate ligands were applied to synthesize one mononuclear and three trinuclear silver complexes including two cyclic "microclusters" and a linear tri-nuclear silanethiolate complex. All obtained compounds are characterized by X-ray diffraction and FT-IR. NMR and emission spectroscopies were used where possible. The first trinuclear anionic silver thiolate is structurally characterized. The influence of the different charge of cyclic silver complexes as well as the overall ligand environment on the structural properties is demonstrated. The impact of the different synthetic routes on the final structures of the obtained clusters - cyclic or linear - is discussed.

Variable-temperature X-ray diffraction study of structural parameters of NH---S hydrogen bonds in triethylammonium and pyridinium silanethiolates.

Two hydrogen-bonded, well defined compounds were synthesized from tris(2,6-diisopropyl)phenoxysilanethiol (TDST) and triethylamine (TDST-TEA) or pyridine (TDST-py). The crystalline compounds were characterized in the solid state by variable-temperature X-ray diffraction measurements and ATR FT-IR spectroscopy. The toluene solutions of TDST-TEA and TDST-py were studied by NMR spectroscopy. The total hydrogen-bond energies and FT-IR spectra were calculated with the use of BLYP-D/TZP and B3LYP/6-31G(d,p)/GD3BJ methods. Thermochemical parameters and potential energy scans were calculated at the B3LYP/6-31G(d,p)/GD3BJ level. All results point to the higher energy of bonding in TDST-TEA both in the solid state and in solution. At the same time the potential energy scan reveals a very broad double-well hydrogen bond in TDST-py, indicating good stabilization of the system for a wide range of D-H...A distances.

Bis(3,5-dimethyl-pyridine-κN)bis-(tri-tert-butoxy-silanethiol-ato-κS)chromium(II) toluene solvate.

In the title chromium silanethiol-ate, [Cr(C(12)H(27)O(3)SSi)(2)(C(7)H(9)N)(2)]·C(7)H(8), the Cr(II) atom is coordinated by two S and two N atoms in a distorted square-planar geometrical arrangement. The mononuclear mol-ecule lies on a twofold axis that passes through the pyridine N atoms. The toluene solvent mol-ecule is equally disordered about a twofold axis.

A study of chirality in bis(1,2-dimethoxyethane-kappa2O,O')sodium bis(tri-tert-butoxysilanethiolato-kappa2O,S)sodate.

This work presents an analysis of self-assembly of a complex molecule from simpler ions, some of which are asymmetric, and is an example of a sodium silanethiolate. The tri-tert-butoxysilanethiolate anion has two helical conformers (P and M), so aggregation of silanethiolates can proceed with recognition of chirality. Alkali metal silanethiolates can form cyclic solvated oligomers (e.g. dimers) or complexes such as sodates with anions of general formula R2Na(-). We note that all known sodates (and lithiates) contain both ligands of the same helicity in the anion, whereas in the dimers the metal atoms are coordinated by silanethiolate ligands of different helicity. The title compound, a new example of a sodate, [Na(C4H10O2)2][Na(C12H27O3SSi)2] or [Na{((t)BuO)3SiS}2][Na(DME)2] (DME is 1,2-dimethoxyethane), is built up of separate ion pairs with no significant interactions. The anion is formed from an Na atom O,S-chelated by two silanethiolate ligands of the same helicity (both P or both M), while the cation contains an Na atom solvated by two DME molecules. Because the structure is centrosymmetric, equal numbers of both conformational enantiomers are present in the crystal lattice.

Bis(di-n-propyl-amine-κN)bis-(tri-tert-butoxy-silanethiol-ato-κS)chromium(II).

The title compound, [Cr(C(12)H(27)O(3)SSi)(2)(C(6)H(15)N)(2)], is a mol-ecular chromium(II) thiol-ate that is coordinated by two dipropyl-amine ligands in a square-planar environment. The mol-ecule lies on an inversion site.

(Mu-tri-tert-butoxysilanethiolato)bis[(tetrahydrofuran)lithium(I)] and catena-poly[[bis(mu-tri-tert-butoxysilanethiolato)dilithium(I)]-mu-dimethoxyethane]: solvent coordination as the structure-forming factor.

The title compounds, mu-(tri-tert-butoxysilanethiolato-kappa2S:S)-bis[(tetrahydrofuran-kappaO)lithium(I)], [Li2(C12H27O3SSi)2(C4H8O)2], (I), and catena-poly[[bis(mu-tri-tert-butoxysilanethiolato)-1:2kappa(2)S;1kappaS:2kappaS,O-dilithium(I)]-mu-dimethoxyethane-kappa2O:O'], [Li2(C12H27O3SSi)2(C4H10O2)]n, (II), were obtained by the reaction of tri-tert-butoxysilanethiol with metallic lithium. The crude product, when recrystallized from tetrahydrofuran (THF) yields (I), and when recrystallized from 1,2-dimethoxyethane (DME) gives (II). Compound (I) forms centrosymmetric dimers in the solid state with an Li2S2 central core, whereas (II) forms infinitely long chains, in which the centrosymmetric dimeric units are linked together by the bidentate DME ligand (also residing on an inversion centre), thus forming a coordination polymer. The formation of a one-dimensional structure in (II) is a consequence of replacement of a monodentate THF solvent molecule with a bidentate DME molecule.