Transition‐Metal‐Induced Rearrangement of [(PhSn)₄S₆] Towards Ternary Cu^I/Sn/S or Cu^II/Sn/S Clusters

Abstract

Direct access of ternary copper‐tin sulfide clusters by reactions of a binary organotin sulfide cluster, [(PhSn)4S6] (A), with transition metal complexes was achieved for the first time without extra addition of further chalcogenide sources. This indicates that an in situ rearrangement of the inorganic core takes place even without initial formation of anionic fragments. The use of [Cu(PPh3)3Cl] or [Cu(PPh3)2Cl2] as reactants yielded the ternary clusters [(CuPPh3)4(PhSn)18Cu6S31Cl2] (1) and [{Cu(PPh3)2}2(PhSn)3(SnCl)S8] (2), respectively. Whereas 1 represents the largest neutral Cu/Sn/S cluster known to date, compound 2, which is the first example of a ternary Cu/Sn/E (E=S, Se) cluster containing copper in the +II oxidation state, may be viewed as a very early stage of cluster formation. Apparently, the presence of CuII inhibits effective cluster growth, which rationalizes the lack of such species so far. The two ternary clusters exhibit very similar optical absorption energies despite their markedly different cluster sizes. According to time‐dependent DFT calculations, this is due to different characters of the electronic excitation in the triplet compound 2, as compared to the excitation of the closed shell cluster 1, which serve to compensate for the different extensions of the clusters.

Behavior of Organotin Sulfide Clusters towards Zinc Compounds

“…The distortion, however, causes all of the four tin atoms to realize the trigonal‐bipyramidal coordination. A similar distortion has recently been observed for an [Sn 4 S 6 ] cage, to which two [Cu(PPh 3 ) 2 ] coordinate, such that two of the tin sites are additionally part of an [SnS 2 Cu] four‐membered ring attached to the original cage …”

Copper nanoclusters: designed synthesis, structural diversity, and multiplatform applications

“…Another example of such phenomenon in the ternary systems with tin has been reported by the group of Stefanie Dehnen by the reaction of binary organotin sulphide cluster [(PhSn)4S6] with [Cu(PPh3)3Cl] (Scheme 1c). 160 The resulting [(CuPPh3)4(PhSn)18Cu6S31] cluster is a pseudo dimer having a [Sn18Cu10S31] core, which is separated in two identical parts connected by a single sulphur atom ( Fig. 9 A).…”

Current advances in tin cluster chemistry

“…4, right). 69 Derivatization of the organic substituents require the presence of organic substituents with suitable functional groups. In most reported cases, condensation reactions between -C]O and -NH 2 groups were applied.…”