Abstract
The isocyanide complexes cis-[MCl2(CNC6H4-4-X)2] (M = Pd; X = Cl, Br; M = Pt; X = Br) form isomorphous crystal structures exhibiting the Cl/Br and Pd/Pt exchanges featuring 1D chains upon crystallisation. Crystal packing is supported by the C–X···X–C halogen bonds (HaBs), C–H···X–C hydrogen bonds (HB), X···M semicoordination, and C···C contacts between the C atoms of aryl isocyanide ligands. The results of DFT calculations and topological analysis indicate that all the above contact types belong to attractive noncovalent interactions. A projection of the electron localization function (ELF) and an inspection of the electron density (ED) and the electrostatic potential (ESP) reveal the amphiphilic nature of X atoms playing the role of HaB donors, HaB and HB acceptors, and a nucleophilic partner in X···M semicoordination.
Highlights
C hydrogen bonds (HB), X···M semicoordination, and C···C contacts between the C atoms of aryl isocyanide ligands
In the course of our previous studies, we have developed a new class of organometallic tectons involving halogen bonds (HaBs), i.e., palladium(II) and platinum(II) complexes with halogensubstituted aryl isocyanides trans-[MX’2 (CNC6 H4 -4-X)2 ] (M = Pd, Pt; X’ = Br, I; X = Cl, Br, I) [16,50,51]
Throughout experimental and theoretical studies [16,50,51], we have shown that halogen atoms in isocyanide ligands (X) have areas with a positive electrostatic potential (ESP) corresponding to a σ-hole position, which makes these halogens potential HaB donors
Summary
C hydrogen bonds (HB), X···M semicoordination, and C···C contacts between the C atoms of aryl isocyanide ligands. Throughout experimental and theoretical studies [16,50,51], we have shown that halogen atoms in isocyanide ligands (X) have areas with a positive ESP corresponding to a σ-hole position, which makes these halogens potential HaB donors. Halides (X’) bonded to a metal centre carry a negative ESP on the whole of their surface and can act solely as HaB acceptors. These metal complexes simultaneously bear two σhD (X) and two σhA (X’) that are oriented perpendicularly. Pursuing our interest in crystal engineering involving halogen bonding and their effect on properties and reactivity
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