Polycentric binding in complexes of trimethylamine-N-oxide with dihalogens

Abstract

Dihalogens readily interact with trimethylamine-N-oxide under ambient conditions. Stable 1 : 1 adducts were obtained in a case of iodine chloride and iodine bromide. Formally monodentate ligands are bound in a polycentric manner.

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“…Also, it was previously indicated that good uncorrected results can be obtained with small basis sets like cc-pVDZ-F12 (tested on S22, S22x5, and S66 benchmark sets for weak interactions), owing to error compensation between basis set superposition error (which overbinds) and intrinsic basis set insufficiency (which underbinds). A study of binding in complexes of trimethylamine- N -oxide with dihalogens, which includes heavy iodine atoms at the DGDZVP level of theory, reveals that basis set superposition error values do not exceed 2 kJ/mol . The small influence of the basis set superposition has also been acknowledged for complexes of iodine and iodine halides and for structures in which the halogen atom is involved in halogen and hydrogen bonding .…”

“…A study of binding in complexes of trimethylamine-N-oxide with dihalogens, which includes heavy iodine atoms at the DGDZVP level of theory, reveals that basis set superposition error values do not exceed 2 kJ/mol. 86 The small influence of the basis set superposition has also been acknowledged for complexes of iodine 87 and iodine halides 88 and for structures in which the halogen atom is involved in halogen and hydrogen bonding. 89 In particular, in a benchmark study focused on astatine compounds, 90 it was shown that accurate equilibrium constants can be predicted using the double-zeta quality basis sets such as the AVDZ one.…”