The synthesis of new functionalized organotin-chalcogenide complexes was achieved by systematic optimization of the reaction conditions. The structures of compounds [(R(1, 2) Sn)3 S4 Cl] (1, 2), [((R(2) Sn)2 SnS4 )2 (μ-S)2 ] (3), [(R(1, 2) Sn)3 Se4 ][SnCl3 ] (4, 5), and [Li(thf)n ][(R(3) Sn)(HR(3) Sn)2 Se4 Cl] (6), in which R(1) =CMe2 CH2 C(O)Me, R(2) =CMe2 CH2 C(NNH2 )Me, and R(3) =CH2 CH2 COO, are based on defect heterocubane scaffolds, as shown by X-ray diffraction, (119) Sn NMR spectroscopy, and ESI mass spectrometry analyses. Compounds 4, 5, and 6 constitute the first examples of defect heterocubane-type metal-chalcogenide complexes that are comprised of selenide ligands. Comprehensive DFT calculations prompted us to search for the formal intermediates [(R(1) SnCl2 )2 (μ-S)] (7) and [(R(1) SnCl)2 (μ-S)2 ] (8), which were isolated and helped to understand the stepwise formation of compounds 1-6.
Reactions of R(1) SnCl3 (R(1) =CMe2 CH2 C(O)Me) with (SiMe3 )2 Se yield a series of organo-functionalized tin selenide clusters, [(SnR(1) )2 SeCl4 ] (1), [(SnR(1) )2 Se2 Cl2 ] (2), [(SnR(1) )3 Se4 Cl] (3), and [(SnR(1) )4 Se6 ] (4), depending on the solvent and ratio of the reactants used. NMR experiments clearly suggest a stepwise formation of 1 through 4 by subsequent condensation steps with the concomitant release of Me3 SiCl. Furthermore, addition of hydrazines to the keto-functionalized clusters leads to the formation of hydrazone derivatives, [(Sn2 (μ-R(3) )(μ-Se)Cl4 ] (5, R(3) =[CMe2 CH2 CMe(NH)]2 ), [(SnR(2) )3 Se4 Cl] (6, R(2) =CMe2 CH2 C(NNH2 )Me), [(SnR(4) )3 Se4 ][SnCl3 ] (7, R(4) =CMe2 CH2 C(NNHPh)Me), [(SnR(2) )4 Se6 ] (8), and [(SnR(4) )4 Se6 ] (9). Upon treatment of 4 with [Cu(PPh3 )3 Cl] and excess (SiMe3 )2 Se, the cluster fragments to form [(R(1) Sn)2 Se2 (CuPPh3 )2 Se2 ] (10), the first discrete Sn/Se/Cu cluster compound reported in the literature. The derivatization reactions indicate fundamental differences between organotin sulfide and organotin selenide chemistry.
Ru II -and Ru III -substituted α-Keggin-type phosphotungstates with a dimethyl sulfoxide (DMSO) ligand, [PW 11 O 39 Ru II DMSO] 5-(1) and [PW 11 O 39 Ru III DMSO] 4-(2), were synthesized. Compound 1 was prepared by reaction of [PW 11 O 39 ] 7with [Ru II (DMSO) 4 ]Cl 2 in water at 125°C under hydrothermal conditions and was isolated as a cesium salt. Compound 2 was prepared by reaction of 1 with bromine in water at 60°C and was isolated as a cesium salt. The compounds were characterized by cyclic voltammetry, elemental analysis, UV/Vis, IR, * Prof. Dr. M. Sadakane
We report the extension of the class of organotetrel sulfide clusters with further examples of the still rare silicon‐based species, synthesized from RSiCl
3
with R=phenyl (Ph,
I
), naphthyl (Np,
II
), and styryl (Sty,
III
) with Na
2
S. Besides known [(PhSi)
4
S
6
] (
IV
), new compounds [(NpSi)
4
S
6
] (
1
) and [(StySi)
4
S
6
] (
2
) were obtained, the first two of which underwent reactions with [AuCl(PPh
3
)] to form ternary complexes. DFT studies of cluster dimers helped us understand the differences between the habit of {Si
4
S
6
}‐ and {Sn
4
S
6
}‐based compounds. Crystalline
1
showed a pronounced nonlinear optical response, while for intrinsically amorphous
2
, the chemical damage threshold seems to inhibit a corresponding observation. Calculations within the independent particle approximation served to rationalize and compare electronic and optical excitations of [(RSi)
4
S
6
] clusters (R=Ph, Np). The calculations reproduced the measured data and allowed for the interpretation of the main spectroscopic features.
We report the extension of the class of organotetrel sulfide clusters with further examples of the still rare silicon‐based species, synthesized from RSiCl3 with R=phenyl (Ph, I), naphthyl (Np, II), and styryl (Sty, III) with Na2S. Besides known [(PhSi)4S6] (IV), new compounds [(NpSi)4S6] (1) and [(StySi)4S6] (2) were obtained, the first two of which underwent reactions with [AuCl(PPh3)] to form ternary complexes. DFT studies of cluster dimers helped us understand the differences between the habit of {Si4S6}‐ and {Sn4S6}‐based compounds. Crystalline 1 showed a pronounced nonlinear optical response, while for intrinsically amorphous 2, the chemical damage threshold seems to inhibit a corresponding observation. Calculations within the independent particle approximation served to rationalize and compare electronic and optical excitations of [(RSi)4S6] clusters (R=Ph, Np). The calculations reproduced the measured data and allowed for the interpretation of the main spectroscopic features.
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