Experimental and theoretical calculations were used to measure the extent of complexation of iron pentacarbonyl, Fe(CO)5, with various ethers and their sulfur analogues. These solvents include dimethyl ether, dimethyl sulfide, dibutyl ether, dibutyl sulfide, tetrahydrofuran (THF) and tetrahydrothiophene. The Fe(CO)5Solvent complex has a signature IR-active vibrational mode (u1) that is temperature dependent and not active in the isolated Fe(CO)5. Analysis of the IR active modes in these complexes through the use of Origin provides a complete thermodynamic description (DHrxn, DSrxn, DGrxn, Keq) of each Fe(CO)5Solvent complexation reaction: Fe(CO)5 + Solvent ↔ Fe(CO)5●Solvent The experimental data was complemented with dispersion corrected density functional theory calculations to determine the optimum distance from the iron center to the solvent molecule. In addition, the molecular orbitals of the Fe(CO)5, the solvent molecule, and their complex were optimized in order to best approximate their affinity for mixing.

Solvent induced structural dynamics of iron pentacarbonyl in ether and thioether solutions

2019 Spring National Meeting

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