Formation and Structural Diversity of Organo‐Functionalized Tin–Silver Selenide Clusters. Issue 62 (16th October 2017)

• Record Type: Journal Article
• Authors: Rinn, Niklas; Guggolz, Lukas; Gries, Katharina; Volz, Kerstin; Senker, Jürgen; Dehnen, Stefanie
• Is Part Of: Chemistry. Volume 23:Issue 62(2017)
• Page Start: 15607
• Page End: 15611
• Publication Date: 2017-10-16
• Subjects: cluster chemistry -- isomers -- organotin -- selenium -- silver; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201703614
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: When reacting the organic functionalized tin selenide clusters [(SnR 1 )3 Se4 Cl] (A, R 1 =CMe2 CH2 C(O)Me) or [(SnR 1 )4 Se6 ] (B ) with (SiMe3 )2 Se and [Ag(PPh3 )3 Cl] at −78 °C in CH2 Cl2, a microcrystalline intermediate (compound1 ) precipitates, which was investigated by magic angle spinning (MAS) NMR spectroscopy, powder X‐ray diffraction (PXRD), energy dispersive X‐ray (EDX) spectroscopy, and quantum chemistry calculations, to derive information about its composition and structure. Compound1 re‐dissolves under reorganization into the organo‐functionalized Ag/Sn/Se cluster compound [Ag6 (μ6 ‐Se)(Ag8 Se12 ){(R 1 Sn)2 Se2 }6 ] (2 ), or the mixed‐valence cluster [(AgPPh3 )2 (Sn II Cl)2 Se2 {(R 1 Sn IV )2 Se2 }2 ] (3 ), depending on the presence or the exclusion of daylight, respectively. The addition of N2 H4 ⋅H2 O to a solution of1 yields selectively [Ag7 (μ7 ‐Se)(Ag7 Se12 ){(R 2 Sn)2 Se2 }6 ] (4, R 2 =CMe2 CH2 C(N2 H2 )Me), the Ag/Sn/Se core of which is isomeric to that of2. 2 –4 were characterized by X‐ray diffraction. NMR spectroscopic studies on solutions of1 indicate the co‐existence of different species. Abstract : Two organotin silver selenide clusters with isomeric ternary cluster cores are obtained depending on whether the organic groups are keto‐functionalized or further transferred into hydrazine units. This work reports on the formation of these two clusters and a third, mixed valence species from the same intermediate under different reaction conditions. The intermediate and the products were studied by a variety of experimental and quantum chemical methods.