Dramatically Enhanced Solubility of Halide‐Containing Organometallic Species in Diiodomethane: The Role of Solvent⋅⋅⋅Complex Halogen Bonding

Abstract

In the current study, we evaluated the solubility of a number of organometallic species and showed that it is noticeably improved in diiodomethane when compared to other haloalkane solvents. The better solvation properties of CH2I2 were associated with the substantially better σ‐hole‐donating ability of this solvent, which results in the formation of uniquely strong solvent–(metal complex) halogen bonding. The strength of the halogen bonding is attenuated by the introduction of additional halogen atoms in the organometallic species owing to the competitive formation of more favourable intermolecular complex–complex halogen bonding. The exceptional solvation properties of diiodomethane and its inertness towards organometallic species make this solvent a good candidate for NMR studies, in particular, for the acquisition of spectra of insensitive spins.

(Isocyano Group π‐Hole)⋅⋅⋅[d‐MII] Interactions of (Isocyanide)[MII] Complexes, in which Positively Charged Metal Centers (d8‐M=Pt, Pd) Act as Nucleophiles

“…The topological analysis of the electron density distribution with the help of the atoms‐in‐molecules method (QTAIM), developed by Bader, was performed by using the Multiwfn program . For investigation of ESP distribution, the full geometry optimization of the structures of complexes [ 4 ] 2+ and [ 5 ] 2+ was carried out at the DFT level of theory by using the M06‐2X functional with the help of Gaussian‐09 program package (this approach was already successfully applied by us in studies of ESP distribution for relevant Pt II /Pd II complexes). The experimental XRD data were used as a starting point for the geometry optimization procedure of structures of complexes [ 4 – 5 ] 2+ (see the Supporting Information, Figure S7).…”

The halogen bond with isocyano carbon reduces isocyanide odor

“…Taking into account our general interest in the isocyanide chemistry (for our relevant review see ref. 21 ) and, in particular, isocyanide involving crystal engineering [22][23][24][25][26] , we focused our efforts on isocyanide species (CNR) featuring potential lp at the C atom. As a model XB acceptor for this study we addressed the isocyanide CNMes because of its broad usage, commercial availability, and excellent solubility in nonpolar solvents.…”

Four‐Center Nodes: Supramolecular Synthons Based on Cyclic Halogen Bonding

“…), and zero or close to zero positive energy density (0.000–0.002 a.u.) in bond critical points (3, −1) for short contacts listed in Table S5 are typical for noncovalent interactions involving halogen atoms . We have defined energies for these contacts according to several procedures proposed by Espinosa et al., Vener et al., and Tsirelson et al .…”

“…Synthetic approach to 1 a – b and 2 aa – ab has been previously described, while for the syntheses of 2 ba – bb and their characterization by FTIR, 1 H, 13 C{ 1 H}, 195 Pt{ 1 H} NMR, and HRESI‐MS see the Supporting Information.…”