Triflate vs Acetonitrile: Understanding the Iron(II)-Based Coordination Chemistry of Tri(quinolin-8-yl)amine

Abstract

In this study, a synthesis route of tri(quinolin-8yl)amine (L), a recent member of the tetradentate tris(2pyridylmethyl)amine (TPA) ligand family, is reported. With the neutral ligand L bound to an iron(II) center in κ 4 mode, two cisoriented coordination sites remain vacant. These can be occupied by coligands such as counterions and solvent molecules. How sensitive this equilibrium can be is most evident if both triflate anions and acetonitrile molecules are available. All three combinations�bis(triflato), bis(acetonitrile), and mixed coligand species�could be characterized by single-crystal X-ray diffraction (SCXRD), which is unique so far for this class of ligand. While at room temperature, the three compounds tend to crystallize concomitantly, the equilibrium can be shifted in favor of the bis(acetonitrile) species by lowering the crystallization temperature. Removed from their mother liquor, the latter is very sensitive to evaporation of the residual solvent, which was observed by powder X-ray diffraction (PXRD) and Mossbauer spectroscopy. The solution behavior of the triflate and acetonitrile species was studied in detail using time-and temperature-resolved UV/vis spectroscopy, Mossbauer spectroscopy of frozen solution, NMR spectroscopy, and magnetic susceptibility measurements. The results indicate a bis(acetonitrile) species in acetonitrile showing a temperature-dependent spin-switching behavior between highand low-spin. In dichloromethane, the results reveal a high-spin bis(triflato) species. In pursuit of understanding the coordination environment equilibria of the [Fe(L)] 2+ complex, a series of compounds with different coligands was prepared and analyzed with SCXRD. The crystal structures indicate that the spin state can be controlled by changing the coordination environment�all of the {N 6 }-coordinated complexes display geometries expected for low-spin species, while any other donor atom in the coligand position induces a shift to the high-spin state. This fundamental study sheds light on the coligand competition of triflate and acetonitrile, and the high number of crystal structures allows further insights into the influence of different coligands on the geometry and spin state of the complexes.

Exclusively Ligand-Redox-Promoted C–H Tertiary Alkylation of Heteroarenes

“…In a moderately coordinating solvent, the triflate easily exchanges with the solvent, which also causes such peak-broadening. 51,52 Moreover, the X-band EPR spectroscopic determination of the iron speciation is in close agreement with the Mossbauer spectroscopic data. A THF glass of the parent sample at 4.2 K clearly evinces the signature of the S = 5/2 Fe(III) species.…”

“…Additionally, 19 F NMR resonance appeared at δ −19 ppm (in CD 3 CN) as a real broad peak. In a moderately coordinating solvent, the triflate easily exchanges with the solvent, which also causes such peak-broadening. , …”