Synthesis, Structures, and Light‐Induced Transformation of Keto‐Functionalized Selenidogermanate Complexes

Abstract

A double-decker (DD) type selenidogermanate complex with C=O functionalized organic decoration, [(R 1 Ge 4 )Se 6 ] (1, R 1 = CMe 2 CH 2 COMe), was synthesized by reaction of R 1 GeCl 3 with Na 2 Se, and subsequently underwent a light-induced transformation reaction to yield [Na(thf) 2 ][(RGe IV ) 2 (RGe III )(Ge III Se)Se 5 ] (2). Similar to the observations reported previously for the Sn/S homologue of 1, the * Prof. Dr. S. Dehnen 1663 product comprises a mixed-valence complex with a newly formed Ge-Ge bond. However, different from the transformation of the tin sulfide complex, the selenidogermanate precursor did not produce a paddlewheel-like dimer of the DD type structure, but led to the formation of a noradamantane (NA) type architecture, which has so far been restricted to the Si/Se and Ge/Te elemental combination.

Functionalized Organotin‐Chalcogenide Complexes That Exhibit Defect Heterocubane Scaffolds: Formation, Synthesis, and Characterization

“…The reason for this difference from the sulfide analogues is most likely due to the lower partial charge of the tin atoms adjacent to the less-electronegative selenium atoms, such that charge compensation by a chlorine ligand is not required; in addition, steric reasons may play a role, so that the binding of more than five ligands onto a tin atom that is bound to three selenium atoms is disfavored, as confirmed by the structures of compounds 6 a and 6 b (see below). On the contrary, for the related complexes [(R 1 Ge) 4 E 6 ], [12] the coordination number increased along the E = S, Se, Te series as a result of the longer Ge À E bonds, thus indicating the delicate influence of the nature of the tetrel atoms in these complexes. In addition, an overall lower stability of the Sn/Se compounds, according to the lower dissociation energy of the SnÀSe bond versus the SnÀS bond (401 and 464 kJ mol À1 , respectively), [19] will favor the formation of crystals with enhanced lattice energies, as anticipated for the ionic compounds.…”

“…Tetracyclohexyltin (d = À97 ppm) was used as reference sample. The MAS speed was changed (10.5,12,15 kHz) to locate the isotropic chemical shifts.…”

“…[11] However, investigations of the rearrangement of the inorganic core itself have not been implied so far, except for those on the unique formation of noradamantane-type structures [(RGe) 4 E 5 ]. [12] Herein, we report the synthesis and characterization of new organotin-chalcogenide complexes with the general formula [(R F Sn) 3 E 4 Cl] (E = S, Se). These complexes exhibit defect heterocubane [Sn 3 E 4 ] scaffolds, which have emerged as a fundamental structural motif during the dynamic processes in solution.…”

Organotin Selenide Clusters and Hybrid Capsules

“…Both [SnCl 3 ] − and Cl − counterions are commonly observed in organotin chalcogenide chemistry with functional ligands. The appearance of these counterions was previously explained by partial (reductive) decomposition of the precursor clusters [(R 1 Sn) 3 Se 4 Cl] precursor (besides oxidized organic molecules) …”

“…The appearance of these counterions was previously explained by partial (reductive) decomposition of the precursor clusters [(R 1 Sn) 3 Se 4 Cl] precursor (besides oxidized organic molecules). [3,6,15] At hird rugby-ball-like capsulew as synthesized by treating [(R 1 Sn) 3 Se 4 Cl] with 1,1'- (1,5-naphthalenediyl)bishydrazine and crystallized as the salts [(m-R 6 ) 3 (Sn 3 Se 4 ) 2 ][SnCl 3 ] 2 ·3 CH 2 Cl 2 and [(m-R 6 ) 3 (Sn 3 Se 4 ) 2 ][SnCl 3 ] 2 ·6.75 CH 2 Cl 2 (5·3 CH 2 Cl 2 and 5·6.75 CH 2 Cl 2 ; R 6 = (CMe 2 CH 2 C(Me)NNH) 2 C 10 H 6 ). In the cation of 5 (see Figure 4), the defect-heterocubane units are eclipsed, with the relativelyr igidl igands( as opposedt ot hose in 4a and 4b), thus forming straight connections from the top to the bottom unit.…”