Molecular designs for expanding the limits of ultralong C-C bonds and ultrashort HH non-bonded contacts

Chemical Communications : Chem Comm
Nilangshu Mandal, Ayan Datta

Abstract

Recent experiments have reported the formation of very long C-C bonds (dC-C > 1.80 Å) and very short HH non-bonded contacts (dHH < 1.5 Å) in several sets of molecules. Both these rare phenomena arise due to specific donor-acceptor interactions and London dispersion interactions respectively. Favorable negative hyperconjugation, namely H2N(lone-pair) → σ*(C-C), creates an ultralong C-C bond in diamino-o-carborane with dC-C > 1.829 Å and a planar amine reminiscent of a transition-state like structure for ammonia inversion. The small and narrow barrier favours rapid inversion through quantum mechanical tunnelling (QMT) and produces a translationally averaged planar amine as observed in the experiments. On the other hand, designing specific confined molecular cavities or chambers like in,in-bis(hydrosilane) or its germanane analogs furnishes an ultrashort HH distance = 1.47 Å and 1.38 Å respectively. The predisposition of such closely placed HH contacts arises from the rather effective attractive dispersion interactions between them. Controlling the strength of the dispersion interactions provides a rich landscape for realizing such close HH distances. Molecular design ably assisted by computational modeling to further tune these i...Continue Reading

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Citations

Mar 7, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Alexis Antoinette Ann DelgadoElfi Kraka
Jun 29, 2021·Chemical Communications : Chem Comm·Alfonso García-MárquezRafael Gramage-Doria

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Methods Mentioned

BETA
NMR
X-ray
inelastic neutron scattering

Software Mentioned

MM2

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