Premium
Ternary Mixed‐Valence Organotin Copper Selenide Clusters
Author(s) -
Rinn Niklas,
Guggolz Lukas,
Lange Jurek,
Chatterjee Sangam,
Block Theresa,
Pöttgen Rainer,
Dehnen Stefanie
Publication year - 2018
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.201705184
Subject(s) - chemistry , selenide , copper , metal , crystallography , valence (chemistry) , selenium , chloride , ternary operation , stereochemistry , organic chemistry , computer science , programming language
Reactions of the organotin selenide chloride clusters [(R 1 Sn IV ) 3 Se 4 Cl] ( A , R 1 =CMe 2 CH 2 C(O)Me) or [(R 1 Sn IV ) 4 Se 6 ] ( B ) with [Cu(PPh 3 ) 3− x Cl x ] yield cluster compounds with different inorganic, mixed‐valence core structures: [Cu 4 Sn II Sn IV 6 Se 12 ], [Cu 2 Sn II 2 Sn IV 4 Se 8 Cl 2 ], [Cu 2 Sn II Sn IV 4 Se 8 ], [Cu 2 Sn II 2 Sn IV 2 Se 4 Cl 4 ], and [Cu 2 Sn IV 2 Se 4 ]. Five of the compounds, namely [(CuPPh 3 ) 2 {(R 1 Sn IV ) 2 Se 4 }] ( 1 ), [(CuPPh 3 ) 2 Sn II {(R 2 Sn IV ) 2 Se 4 } 2 ] ( 2 ), [(CuPPh 3 ) 2 (Sn II Cl) 2 {(RSn IV ) 2 Se 4 } 2 ] ( 3 ) [(CuPPh 3 ) 2 (Sn II Cu 2 ){(R 1 Sn IV ) 2 Se 4 } 3 ] ( 4 ), and [Cu(CuPPh 3 )(Sn II Cu 2 ){(R 1 Sn IV ) 2 Se 4 } 3 ] ( 5 ) are structurally closely related. They are based on [(CuPPh 3 ) 2 {(RSn IV ) 2 Se 4 } n ] aggregates comprising [(RSn IV ) 2 Se 4 ] and [CuPPh 3 ] building units, which are linked by further metal atoms. A sixth compound, [(CuPPh 3 ) 2 (Sn II Cl) 2 {(R 1 Sn IV Cl)Se 2 } 2 ] ( 6 ), differs from the others by containing [(RSn IV Cl)Se 2 ] units instead, which affects the absorption properties. The compounds were analyzed by single‐crystal X‐ray diffraction, NMR and 119 Sn Mössbauer spectroscopy, DFT calculations as well as optical absorption experiments.