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.

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The dihalomethanes CH 2 X 2 (X = Cl, Br,I )w ere cocrystallizedw ith the isocyanide complexes trans-[MX M 2 (CNC 6 H 4 -4-X C ) 2 ]( M= Pd, Pt;X M = Br,I ;X C = F, Cl, Br) to give an extended series comprising 15 X-ray structures of isostructural adducts featuring 1D metal-involving hexagonlike arrays. In these structures, CH 2 X 2 behavea sb ent bifunctional XB/XB-donating building blocks, whereas trans-ct as al inear XB/XB acceptors. Results of DFT calculations indicate that all XCH 2 -X···X M -M contacts are typical noncovalent interactions with estimated strengthsi nt he range of 1.3-3.2 kcal mol À1 .ACCDC search reveals that hexagon-likea rrays are rather commonb ut previously overlooked structural motives for adducts of transbis(halide) complexesand halomethanes.Figure 7. Aview of LIHMEXc rystal structure with hexagon-like fragment;additionally Pt···I interactions are shown.Figure 8. The Scheme of CSD search of structures with Y'···X-CH 2 -X···Y contacts( a), and structures with hexagonal-like fragments (b).

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.

No abstract