Premium
Stannylium Ions, a Tin(II) Arene Complex, and a Tin Dication Stabilized by Weakly Coordinating Anions
Author(s) -
Schäfer Annemarie,
Winter Florian,
Saak Wolfgang,
Haase Detlev,
Pöttgen Rainer,
Müller Thomas
Publication year - 2011
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.201101938
Subject(s) - natural bond orbital , tin , chemistry , dication , reactivity (psychology) , crystallography , toluene , molecule , salt (chemistry) , ion , nuclear magnetic resonance spectroscopy , atoms in molecules , inorganic chemistry , stereochemistry , organic chemistry , medicine , alternative medicine , pathology
The reactivity of aryl‐substituted stannylenes, Ar 2 Sn ( 4 ), towards silylarenium borates, [R 3 SiArH][B(C 6 F 5 ) 4 ] ( 3 ), was investigated. The reaction with 2,3,4‐trimethyl‐6‐ tert ‐butylphenyl (mebp)‐substituted stannylene gave silyl‐substituted stannylium ions 2 a , b , which were characterized by NMR spectroscopy supported by the results of quantum‐mechanical computations of molecular structures and magnetic properties. The tri‐ iso ‐propylphenyl‐substituted stannylium ions 2 c , d undergo a decomposition reaction in toluene to give the dicationic tin–arene complex [Sn(C 7 H 8 ) 3 ] 2+ ( 5 ) in the form of the [B(C 6 F 5 ) 4 ] salt in high yields. The 5 [B(C 6 F 5 ) 4 ] 2 salt was identified by single crystal X‐ray diffraction analysis and by Mössbauer spectroscopy. The bonding situation was investigated by using natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) calculations. The substitution of the weakly coordinating borate anion by the carboranate [CB 11 H 6 Br 6 ] − results in replacement of the toluene ligands and formation of tin(II) carboranate with only weak Sn 2+ –anion interactions as suggested by the solid‐state structure of the isolated salt.