Alkali metal cation complexation and solvent interactions by robust chromium(III) fluoride complexes

Interaction of robust chromium(III) fluoride complexes with sodium or lithium cations in solution lead to hypsochromic spectral shifts of increasing magnitude along the series: trans-[CrF2(py)4]+, mer-[CrF3(terpy)], and fac-[CrF3(Me3tacn)]. Crystalline products isolated from solution exhibit μ2-bridging by the fluoride ligands in a linear fashion between Na+-ions and chromium centres in catena-[Na(H2O)4(μ-F)-trans-{CrF(py)4}](HCO3)2 and in the dimers [Li(H2O)n(μ-F)-trans-{CrF(py)4}]2+ (n = 3, 4). The uncharged chromium complexes fac-[CrF3(Me3tacn)] and mer-[CrF3(terpy)] have been synthesized from mer-[CrF3(py)3] and shown to precipitate sodium salts from solution, of which 3[CrF3(Me3tacn)]·2Na(Bph4)·solv and 6[CrF3(terpy)]·4Na(Bph4)·solv have been crystallographically characterized. In these clusters, the neutral fluoride complexes bring the Na+ cation separation down to 3.610 Å and 3.369 Å, respectively, which is much closer than the inter-cation distance in NaCl and comparable to that of NaF. DFT calculations support the notion of a strong interaction between Na+ ions and neutral chromium(III) fluoride complexes. The calculations reproduce the magnitude and the counter-intuitive sign of the spectral shifts induced by second sphere complexation in solution, which originates in a breakdown of the assumption of parameter transferability in ligand-field descriptions.

Cationic and uncharged chromium(III)fluoride complexes interact strongly with alkali metal ions in solution as well as in the solid state. This leads to a new structure type of fluoride-bridged clusters. Spectroscopic effects of second sphere interactions are modeled and interpreted by use of DFT calculations.Figure optionsDownload as PowerPoint slide