The Coordination Chemistry of the CF Group of Fluorocarbons: Thermodynamic Data and Ab Initio Calculations on CF-Metal Ion Interactions

Abstract

(26-fluoro-4,7,13,16-tetraoxa-1,10-diaza-tricyclo[8.8.7.1,20,24]hexacosa-20,22,24(26)-triene and 4,7,13,16-tetraoxa-1,10-diazatricyclo[8.8.7.1,20,24]

Perturbation of 1JC,F Coupling in Carbon–Fluorine Bonds on Coordination to Lewis Acids: A Structural, Spectroscopic, and Computational Study

“…Reflecting their coordination to a metal center, each of these C-F bonds are elongated by a small but significant distance (avg. 0.025 Å) relative to their corresponding unbound C-F bonds, a phenomenon that has been predicted computationally 22 and observed in other systems with C-F … Li interactions evident in the solid-state. 15,16…”

Molecular Simulations of Fatty‐Acid Methyl Esters and Representative Biodiesel Mixtures

“…Examples of fluorocarbon coordination are known for metals in every block (s, p, d, f) of the periodic system 4. The RF→M interaction is, in general, weak,6 but may exert a distinct stabilizing or protective effect,7 often influencing the activity of some metal‐based catalytic systems 7b. Interestingly, Schelter and co‐workers have recently found that RF→M interactions (Scheme ; X=H, F) can also forge the coordination sphere of f elements, thereby enabling quite unusual geometries 8…”

Bond energy enabled amine distinguishing strategy: chemo-, regioselective 1,3-diamination of (trifluoromethyl)alkenes with different amines by two C(sp3)–F bond cleavages

“…The interaction between the alkali-metal ion and the fluorine atom might favor the leaving of fluoride in the ipso-selective defluorinative amination step. 27 Importantly, the success of this reaction arises from the different bond energies of the sequentially cleaved C(sp 3 )-F bonds, which enables the sequential ipso-/γ-selective defluorinative amination process of the reaction pathway. The different priority of the amine nucleophiles involved in these two different steps enables the distinguishing of the two amines.…”