Solution and Gas-Phase Investigations of Trimethylsilylpropyl-Substituted Pyridinium Ions. Manifestation of the Silicon delta Effect
Asimo Karnezis, Richard AJ O'Hair, Jonathan M White
ORGANOMETALLICS | AMER CHEMICAL SOC | Published : 2011
Computational studies on the N-methyl-2-trimethyl- M-propylpyridinium ions 15a (M = Si), 15b (M = Ge), 15c (M = Sn), and 15d (M = Pb) and N-methyl-4-trimethyl-Mpropylpyridinium ions 16a (M = Si), 16b (M = Ge), 16c (M = Sn), and 16d (M = Pb) provide evidence for a significant through-bond (double hyperconjugative) interaction between the M-CH2 bond and the low-lying π* orbital of the pyridinium ion. The strength of this interaction increases in the order Si < Ge < Sn < Pb, in line with the σ-donor abilities of the C-M bond. The through-bond interaction for M = Si has been studied in solution using 13C and 29Si NMR studies; however, the effect is small. The collision-induced dissociation fragm..View full abstract
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Awarded by Australian Research Council
We thank the Australian Research Council for financial support (DP0770565) and an award of an APA to A.K. We also thank the Victorian Partnership for Advanced Computing and the Victorian Institute for Chemical Sciences High Performance Computing Facility for computational time.