Organometallic halogen bond acceptors: directionality, hybrid cocrystal precipitation, and blueshifted CO ligand vibrational band

Abstract

The halogen bonding (XB) in metal carbonyls blueshifts the νCO band and XB directionality is dictated by XB-accepting atom hybridization.

Halogen-bonded cocrystallization with phosphorus, arsenic and antimony acceptors

“…Compared to hydrogen bonding, XB is expected to provide access to molecular assembly motifs involving heavy atoms with increasingly diffuse electron orbitals, that would engage in hydrogen bonding only with difficulty or not at all 7 . This is shown in reports of XB cocrystals involving later members of group 16, e.g., S, Se, and, most recently, Te 8–12 . In contrast, until recently 13 there have been no reports of analogous cocrystals of group 15 elements (the pnictogens) except nitrogen 14–16 , and documented examples of XB interactions to heavier pnictogens appear limited to gas-phase studies.…”

Synthesis and Characterization of Bidentate Isonitrile Iron Complexes

“…The carbon monoxide analogue I shows a similar distorted tetrahedral geometry in which the chloride and the two CO ligands are sterically repelled by the η 5coordinated cyclopentadienyl ligand and possess C−Fe−C angles of 95.6(2)° and C−Fe−Cl angles of 90.4(2)° (vs. angles in 3: C1−Fe−C20 88.4 (7), C1−Fe−Cl 94.3 (6); C20−Fe−Cl 91.4 (6)). [32] The 31 P{ 1 H} NMR spectrum of 3 gives rise to a sharp singlet at δ = 15.2 ppm. The IR spectrum shows two broad bands at 2084 and 2023 cm −1 , which are assigned to the symmetrical and asymmetrical CN stretching vibrations.…”

The combination of halogen and hydrogen bonding: a versatile tool in coordination chemistry

“…5 The intermolecular interactions include hydrogen bonds, 6,7 -stacking interactions and, more recently -and thus much less explored, halogen bonding interactions. 8,9,10,11,12 In order to utilize the structure-directing abilities of hydrogen and halogens bonds in coordination chemistry we have prepare 4-iodo-N-(4-pyridyl)benzamide (INPBA) (Chart 1) and metal complexes with this ligand and Ag + , Zn 2+ and Hg 2+ metal ions.…”