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Crystalline Molecular Complexes and CompoundsStructures and Principles$
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Frank H. Herbstein

Print publication date: 2005

Print ISBN-13: 9780198526605

Published to Oxford Scholarship Online: September 2007

DOI: 10.1093/acprof:oso/9780198526605.001.0001

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Donor–acceptor molecular compounds (essentially localized interactions)

Donor–acceptor molecular compounds (essentially localized interactions)

Chapter 11 Donor–acceptor molecular compounds (essentially localized interactions)
Crystalline Molecular Complexes and Compounds

Frank H. Herbstein

Oxford University Press

This chapter discusses components that are linked mainly by localized interactions. There is a variety of donor and acceptor types ranging from n-Donors and σ*-Acceptors, through n-Donors and p-Acceptors, n-Donors and p*-Acceptors, π-Donors and s,p-Acceptors to p-Donors and σ*-Acceptors. The first of these categories includes some self-complexes. A distinction has been made between ‘pure acceptors’ and ‘self-interacting acceptors’. The ‘pure acceptors’ are involved only in donor-acceptor interaction with the donor component of the molecular compound. In the ‘self-interacting acceptors’, the principal acceptor atom (e.g., Ag+ in AgClO4 or Sb in SbCl3), in addition to its donor-acceptor interaction, is also involved in interactions with other atoms of the acceptor moiety (e.g., the oxygens of AgClO4 or chlorines of SbCl3). These additional interactions are essential to the stability of the crystalline molecular compounds. Despite widespread use of the term ‘charge transfer’ to describe these compounds, physical measurements (e.g., NQR, Mössbauer effect) suggest that there is very little actual transfer of charge in the ground state, as Mulliken often emphasized.

Keywords:   localized interactions, pure acceptors, self-interacting acceptors, Menscutkin complexes

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