Ternary Mixed‐Valence Organotin Copper Selenide Clusters

Abstract

Reactions of the organotin selenide chloride clusters [(R Sn ) Se Cl] (A, R =CMe CH C(O)Me) or [(R Sn ) Se ] (B) with [Cu(PPh ) Cl ] yield cluster compounds with different inorganic, mixed-valence core structures: [Cu Sn Sn Se ], [Cu Sn Sn Se Cl ], [Cu Sn Sn Se ], [Cu Sn Sn Se Cl ], and [Cu Sn Se ]. Five of the compounds, namely [(CuPPh ) {(R Sn ) Se }] (1), [(CuPPh ) Sn {(R Sn ) Se } ] (2), [(CuPPh ) (Sn Cl) {(RSn ) Se } ] (3) [(CuPPh ) (Sn Cu ){(R Sn ) Se } ] (4), and [Cu(CuPPh )(Sn Cu ){(R Sn ) Se } ] (5) are structurally closely related. They are based on [(CuPPh ) {(RSn ) Se } ] aggregates comprising [(RSn ) Se ] and [CuPPh ] building units, which are linked by further metal atoms. A sixth compound, [(CuPPh ) (Sn Cl) {(R Sn Cl)Se } ] (6), differs from the others by containing [(RSn Cl)Se ] units instead, which affects the absorption properties. The compounds were analyzed by single-crystal X-ray diffraction, NMR and Sn Mössbauer spectroscopy, DFT calculations as well as optical absorption experiments.

Transition‐Metal‐Induced Rearrangement of [(PhSn)4S6] Towards Ternary CuI/Sn/S or CuII/Sn/S Clusters

“…2 is a rare example of a ternary Cu/Sn/E (E=chalcogenide) cluster featuring Cu II , and actually the first one for E=S, Se. In similar reactions employing [Cu(PPh 3 ) 2 Cl 2 ], reduction of the copper ions to the +I oxidation state was always observed, although there are examples for mixed‐valent copper chalcogenide clusters, predominantly with tellurium atoms acting as bridging ligands . The observation of the copper ions in their original oxidation state, despite the reductive environment of sulfide ions and phosphine molecules, may be due to the immatureness of the cluster; apparently, it has just passed the first step of cluster growth, such that reduction has not yet occurred, but would be the next step.…”

Current advances in tin cluster chemistry

“…59 65 Organotin chalcogenide clusters can serve as starting ground for follow-up reactions, either by extension of their inorganic core, or by derivatization of their organic substituents. Modications of the inorganic core are usually achieved by reactions 55 and Cu,Ag/Se 67,68 ), but also large clusters like the isomeric species [(RSn) 12 Ag 14 Se 25 ] with R ¼ CMe 2 CH 2 CO(Me) (Fig. 4, le) or R ¼ CMe 2 CH 2 CNNH 2 (Me), 67 or the cluster [(PhSn) 18 Cu 10 S 31 (PPh 3 ) 4 Cl 2 ] (Fig.…”

Systematic Access of Ternary Organotetrel‐Copper Chalcogenide Clusters by [PhTE3]3− Anions (T=Si, Sn; E=S, Se)

“… [32] Regarding organo‐functionalized clusters, a synthesis from mononuclear compounds is possible, [33] but most of the reported clusters were synthesized by transformations of binary cage compounds of the general formulas [(RSn) 4 E 6 ] or [(RSn) 3 E 4 Cl] (R=organic substituent, E=S, Se). [ 34 , 35 , 36 , 37 , 38 , 39 , 40 ] One of the first compounds of this type, [(CuPPhMe 2 ) 6 (PhSnS 3 ) 2 ], [40] was synthesized by using [Cu(PPhMe 2 )bipyCl] (bipy=2,2’‐bipyridine) as the source of Cu atoms, while fragmentation of the heteroadamantane compound [(PhSn) 4 S 6 ] with Na 2 S formed [PhSnS 3 ] 3− in situ, as the source of the RSn units. [41] This was the first example of the inorganic cluster core archetype [(CuPPh 3‐x R′ x ) 6 (RTE 3 ) 2 ] (x=0, 1, 2), consisting of six Cu atoms arranged in a chair conformation that is connected to two TE 3 groups to obtain an overall spherical architecture.…”

“… [38] The synthetic protocol was expanded for clusters comprising coinage metal atoms to the Ge congeners and to corresponding Ag and Au compounds. [ 34 , 36 , 37 , 38 , 48 , 49 , 50 , 51 , 52 , 53 ] A combined organic‐inorganic extension of the substituents was possible by decoration of clusters with metallocenes,[ 49 , 54 , 55 , 56 , 57 , 58 , 59 ] or with chelate ligands to trap transition metals from solution. [60] To the best of our knowledge, corresponding ternary Si clusters have not yet been reported in the literature.…”