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Formation and Structural Diversity of Organo‐Functionalized Tin–Silver Selenide Clusters
Author(s) -
Rinn Niklas,
Guggolz Lukas,
Gries Katharina,
Volz Kerstin,
Senker Jürgen,
Dehnen Stefanie
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201703614
Subject(s) - selenide , crystallography , tin , powder diffraction , microcrystalline , magic angle spinning , chemistry , spectroscopy , cluster (spacecraft) , nuclear magnetic resonance spectroscopy , valence (chemistry) , materials science , selenium , stereochemistry , physics , organic chemistry , quantum mechanics , computer science , programming language
Abstract When reacting the organic functionalized tin selenide clusters [(SnR 1 ) 3 Se 4 Cl] ( A , R 1 =CMe 2 CH 2 C(O)Me) or [(SnR 1 ) 4 Se 6 ] ( B ) with (SiMe 3 ) 2 Se and [Ag(PPh 3 ) 3 Cl] at −78 °C in CH 2 Cl 2 , a microcrystalline intermediate (compound 1 ) 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. Compound 1 re‐dissolves under reorganization into the organo‐functionalized Ag/Sn/Se cluster compound [Ag 6 (μ 6 ‐Se)(Ag 8 Se 12 ){(R 1 Sn) 2 Se 2 } 6 ] ( 2 ), or the mixed‐valence cluster [(AgPPh 3 ) 2 (Sn II Cl) 2 Se 2 {(R 1 Sn IV ) 2 Se 2 } 2 ] ( 3 ), depending on the presence or the exclusion of daylight, respectively. The addition of N 2 H 4 ⋅H 2 O to a solution of 1 yields selectively [Ag 7 (μ 7 ‐Se)(Ag 7 Se 12 ){(R 2 Sn) 2 Se 2 } 6 ] ( 4 , R 2 =CMe 2 CH 2 C(N 2 H 2 )Me), the Ag/Sn/Se core of which is isomeric to that of 2. 2 – 4 were characterized by X‐ray diffraction. NMR spectroscopic studies on solutions of 1 indicate the co‐existence of different species.