Prereactive Complexes of Dihalogens XY with Lewis Bases B in the Gas Phase: A Systematic Case for the Halogen Analogue B⋅⋅⋅XY of the Hydrogen Bond B⋅⋅⋅HX

Abstract

Similar and yet also notably different are the B small middle dot small middle dot small middle dotXY and B small middle dot small middle dot small middle dotHX complexes in the gas phase, where B is a simple Lewis base, XY is a homo- or heterodihalogen molecule, and HX is a hydrogen halide. This is demonstrated, for example, by the structures of oxirane small middle dot small middle dot small middle dotClF and oxirane small middle dot small middle dot small middle dotHCl (see picture). Both bonds are dominated by simple electrostatic interactions, but differ in terms of their propensity for nonlinearity.

Isomorphous Crystals from Diynes and Bromodiynes Involved in Hydrogen and Halogen Bonds

“…Scientists exploit supramolecular chemistry (bottom-up strategy) to achieve this goal and control the organization of molecules into diverse 1D [2][3][4], 2D [5][6][7][8][9] or 3D shapes [10][11][12]. Owing to their directional potential, hydrogen bond [13][14][15][16][17][18][19][20][21][22][23] or halogen bond [24][25][26][27][28][29][30][31][32][33][34][35][36] are intermolecular forces that are often used to stick molecular building blocks together. Recently, in our laboratories, we exploited mainly H bonds to build supramolecular walls based on lactams [37] or proline derivatives [38].…”

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

“…It can now easily be recognized as a halogen-bonded or more specifically a chlorine-bonded complex, and Cl is less electronegative than F (i.e., Cl carries a partial positive charge in ClF and is the acceptor of electron density from F of HF). Halogen-bonded systems have been receiving significant attention over the last decade [92,93]. It is important to realize that HFؒؒؒClF, and more importantly HFؒؒؒHF, may be called fluorinebonded except that no one uses such a terminology!…”

Halogen Bonding with Phosphine: Evidence for Mulliken Inner Complexes and the Importance of Relaxation Energy

“…The interactions of simple Lewis bases B with homo-and hetero-dihalogen molecules XY have been systematically studied by rotational spectroscopy over an extended period, 3,32 and the properties of B· · · XY determined in these investigations are those of the isolated complex in the gas phase. method.…”