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 CH I 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.

Halogen Bonding in Isostructural Co(II) Complexes with 2-Halopyridines

“…Regarding all of the approaches in the field of crystal engineering, halogen bonding (XB) has attracted great interest within modern research [1,2]. This type of non-covalent interaction involving halogen atoms (according to the IUPAC-approved definition, the bond "occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity") becomes especially prominent in a solid state, and its appearance can affect numerous physical properties of matter, such as luminescence [3][4][5], solubility [6], color [7], and so forth, therefore providing an additional tool for material design [8][9][10].…”

Antimony(V) Bromide and Polybromide Complexes with N‐alkylated Quinolinium or Isoquinolinium Cations: Substituent‐dependent Assembly of Polymeric Frameworks

“…In order to estimate the energies of the Br ··· Br interactions, we performed DFT calculations and topological analysis of the electron density distribution (QTAIM method) for 1 and 3 (the structure of 2 was excluded from consideration due to disordering). This approach was used by us for other polyhalogen‐halometalates, as well as by other researchers when examining various non‐covalent interactions . Results are presented in Table ; the contour line diagrams of the Laplacian distribution ∇2ρ(r), bond paths, and selected zero‐flux surfaces as well as reduced density gradient (RDG) isosurfaces for Br ··· Br in supramolecular structures of 1 and 3 are shown in Figure and Figure .…”

New Crystal Forms for Biologically Active Compounds. Part 1: Noncovalent Interactions in Adducts of Nevirapine with XB Donors

“…In order to confirm or disprove the hypothesis on the existence of these supramolecular contacts and quantify their energies from a theoretical standpoint, we carried out DFT calculations and performed topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method) [73] for the (NVP) 4 •(1,4-FIB) 3 and (NVP) 3 •(1,3-DIB) 3 model supramolecular cluster (Supporting Information, Table S3). We have already used a similar approach to study noncovalent interactions (e.g., hydrogen, halogen and chalcogen bonding, metallophilic interactions, stacking) in various organic, organometallic and coordination compounds [42][43][44][86][87][88][89]. The results of these calculations are summarized in Table 2 Table 2.…”

“…Considering that over the last decade, the halogen bond (XB) [21] has emerged as an effective tool for crystal engineering [22][23][24][25][26][27][28][29] and designing supramolecular constructs [30][31][32], it is surprising that literature reports on the utility of XB in engineering new API crystal forms has been relatively scarce [20,[33][34][35][36]. Our recent engagement in crystal engineering based on XB in metal complexes [37][38][39][40][41][42][43][44][45] prompted us to consider exploring new opportunities for filling the above void and applying the XB approach towards identifying novel API crystal forms. We screened a number of important APIs for the formation of co-crystals with known potential as well as recently synthesized [46] donors of halogen bonds.…”