Properties of the Halogen−Hydride Interaction:  An ab Initio and “Atoms in Molecules” Analysis

Abstract

X-Cl...H-Y interactions are analyzed by applying ab initio methods as well as the Bader theory. All calculations were performed using Pople's basis sets (6-311++G(2df,2pd) and 6-311++G(3df,3pd)) as well as the Dunning-type bases (aug-cc-pVDZ and aug-cc-pVTZ) within the MP2 method. For the complexes analyzed here, X-Cl and H-Y may be treated as a Lewis acid and a Lewis base, respectively. The Cl...H interactions are rather weak or at most moderate since, for the strongest interaction of the F3...HLi complex, the binding energy calculated at the MP2/6-311++G(3df,3pd) level of approximation amounts to -3.4 kcal/mol, and the H...Cl distance is equal to 2.65 A, less than the corresponding sum of van der Waals radii. These interactions may be classified as halogen-hydride interactions. However, some of the complexes analyzed, especially F3SiCl...HBeF and F3SiCl...HBeF, are very weakly bound, probably by typical van der Waals interactions.

Defining the hydrogen bond: An account (IUPAC Technical Report)

“…It is important to realize that HFؒؒؒClF, and more importantly HFؒؒؒHF, may be called fluorinebonded except that no one uses such a terminology! Similarly, there are examples reported recently in which hydrides act as halogen bond acceptors such as LiHؒؒؒClCF 3 [94]. These are better characterized as halogen-bonded rather than hydrogen-bonded, though H is indeed bonded to two atoms here as well and it would fit Pimentel and McClellan's definition of a hydrogen bond [3].…”

SAPT: ligação de hidrogênio ou interação de van der Waals?

“…Apesar do conhecimento das propriedades teóricas das ligações de hidrogênio, 41 outras importantes interações como as ligações de di-hidrogênio, 42 ligações de hidreto, 43 ligações agósticas, 44 ligações de halogênio, 45 ligações halogênio-hidreto 46 e stacking 47,48 foram consideradas por Lipkowski et al 49 como parte integrante do conjunto de ligações intermoleculares mais moderno até então registrado na literatura. Sabe-se que estas interações atingem um grau de abrangência bastante inusitado.…”

Binuclear Copper(I) Borohydride Complex Containing Bridging Bis(diphenylphosphino) Methane Ligands: Polymorphic Structures of [(µ2-dppm)2Cu2(η2-BH4)2] Dichloromethane Solvate

“…The angles (∠C-H···Cl) for these interactions vary from 145.9 to 149.6 • and H···Cl distances are in the range 2.659-2.679 Å that is less than the sum of van der Waals radii for these two atoms (2.95 Å). There is also a short B-H···Cl-C distance 2.755 Å between BH and DCM with angle ∠C-Cl···H(B) = 158.2 • that resembles a halogen bonding [106,107] and was referred to as a hydride-halogen bond [108][109][110][111][112][113]. This interaction has a donor-acceptor nature, where B-H δ− acts as a donor of electron density and interacts with an electron deficient area (σ-hole) located on the halogen atom +δ Hal-R.…”