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The First Examples of a Crown Ether Intramolecularly Encapsulating Mono‐ and Diorganotin Dications: Synthesis and Structures of [PhSnCH 2 ([16]crown‐5)][ClO 4 ] 2 and [HOSnCH 2 ([16]crown‐5)][Y] 2 (Y=ClO 4 , CF 3 SO 3 )
Author(s) -
Tagne Kuate Alain Charly,
Schürmann Markus,
Schollmeyer Dieter,
Hiller Wolf,
Jurkschat Klaus
Publication year - 2010
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.200903572
Subject(s) - chemistry , crown ether , dication , pentagonal bipyramidal molecular geometry , crystallography , trigonal bipyramidal molecular geometry , bipyramid , nuclear magnetic resonance spectroscopy , monomer , crystal structure , x ray crystallography , perchlorate , stereochemistry , molecule , ion , diffraction , organic chemistry , polymer , physics , optics
The reaction of silver perchlorate with [PhI 2 SnCH 2 ([16]crown‐5)] ( 1 ) and [I 3 SnCH 2 ([16]crown‐5)] ( 2 ) gave the organotin(IV)‐substituted crown ether complexes [PhSnCH 2 ([16]crown‐5)][ClO 4 ] 2 ( 3 ) and [HOSnCH 2 ([16]crown‐5)][Y] 2 ( 4 : Y=ClO 4 , 5 : Y=CF 3 SO 3 ), respectively. All compounds have been isolated as air‐stable materials and characterised by 1 H, 13 C, 119 Sn and 119 Sn MAS ( 5 ) NMR spectroscopy, ESIMS spectrometry, elemental analysis and by single‐crystal X‐ray diffraction analysis. The molecular structures of 3 – 5 show that the tin(IV) cation fits perfectly into the crown ether cavity and is coordinated by the five oxygen atoms of the ring to give a pentagonal bipyramidal configuration about the central metal cation. Notably, compounds 4 and 5 contain the first monomeric monoorganotin dication. Moreover, there are 3 J ( 1 H, 119 Sn) coupling constants to the CH 2 C H proton of 377 ( 3 ) and 470 Hz ( 4 , 5 ) that are, to the best of our knowledge, the biggest such couplings ever reported.