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.
A unique hydrido phosphine-borane iron(II) complex [(dppa)(Ph₂P-N-P(BH₃)Ph₂)Fe(H)] (1) was obtained by the reaction of iron(II) chloride and two equivalents of bis(diphenylphosphino)amine (dppa) with an excess of sodium borohydride in acetonitrile-ethanol mixtures. Detailed investigations of the reaction revealed that a mixture of cis- and trans-[(dppa)₂Fe(NCMe)₂]²⁺ is formed prior to the reduction by sodium borohydride. Depending on the solvent, different products were obtained by the reduction: in acetonitrile-ethanol mixtures the hydrido phosphine-borane complex 1 is formed by formal insertion of BH₃, while the reduction in pure acetonitrile results in the formation of the cationic complex trans-[(dppa)₂Fe(H)(NCMe)](BH₄) (4). Complex 4 is remarkably stable in ethanol and does not undergo phosphine-borane formation, even in the presence of excess sodium borohydride. This observation suggests that the phosphine-borane complex is generated by the reaction with the first equivalent of sodium borohydride with the participation of ethanol, followed by deprotonation or dihydrogen elimination. Experiments with similar diphosphine ligands, such as bis(diphenylphosphino)methane, did not yield a phosphine-borane complex, indicating the crucial role of the amine group in the observed reactivity.
Several compounds with unique structural motifs that have already been known from organotin sulfide chemistry, but remained unprecedented in organotin selenide chemistry so far, have been synthesized. The reaction of [(R Sn) Se ] (R =CMe CH C(O)Me) with N H ⋅H O/(SiMe ) Se and PhN H /(SiMe ) Se led to the formation of [{(R Sn) SnSe } (μ-Se) ] (1; R =CMe CH C(Me)NNH ) and [{(R Sn) SnSe } (μ-Se) ] (2; R =CMe CH C(Me)NNPhH)). The addition of ortho-phthalaldehyde to [(R Sn) Se ] yielded a cluster with intramolecular bridging of the organic groups, namely, [(R Sn ) Se ] (3; R =(CMe CH C(Me)NNCH) C H ). The introduction of organic ligands with longer chains finally allowed the isolation of inorganic-organic capsules of the type [(μ-R) (Sn Se ) ]X , with R=(CMe CH C(Me)NNHC(O)) (CH ) and X=[SnC ], Cl (4 a, b) or R=CMe CH C(Me)NNH) and X=[SnCl ] (5). The capsules enclose solvent molecules and/or anions as guests. All compounds were characterized by means of single-crystal X-ray diffraction studies, NMR spectroscopy, and mass spectrometry.
Clusterchemie. Im Forschungsartikel auf S. 1196 berichten Simone Sanna, Sangam Chatterjee, Doreen Mollenhauer, Stefanie Dehnen et al. über Untersuchungen der weitgehend unerforschten Siliciumchalkogenid‐Cluster [(RSi)4S6] und deren Reaktion mit [AuCl(PPh3)].
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