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Tris(chalcogenato)carbenium Ions [C(XR) 3 ] + (X O, S, Se, Te): An Experimental and Quantum‐Chemical Comparison
Author(s) -
Ohlmann Dietmar,
Marchand Christina M.,
Grützmacher Hansjörg,
Chen Grace Shiahuy,
Farmer David,
Glaser Rainer,
Currao Antonio,
Nesper Reinhard,
Pritzkow Hans
Publication year - 1996
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199603001
Subject(s) - ion , quantum chemical , tris , chemistry , physics , crystallography , molecule , organic chemistry , biochemistry
[C(OR) 3 ] + ions are stabilized differently than [C(XR) 3 ] + ions (X = S, Se, Te). While the stability of the RO‐substituted carbenium ions can be attributed to the high polarity of the C δ+ ‐O δ− bond, the polarity of the C‐X bond in the homologous S‐, Se‐, and Te‐containing ions is reversed, and the stabilization is achieved by the σ‐and π‐dative effect of the chalcogen centers. These results were obtained by ab initio calculations on [C(XH) 3 ] + ions and by experimental studies on the new compounds [C(XR) 3 ][PF 6 ] (X = S, Se, Te; R = 2,4,6‐ i Pr 3 C 6 H 2 ).