Electronic structures of halogenated ruthenium porphyrins. Crystal structure of RuTFPPCl{sub 8}(CO)H{sub 2}O (TFPPCl{sub 8} = octa-{beta}-chlorotetrakis(pentafluorophenyl)porphyrin)
- California Institute of Technology, Pasadena (United States); and others
Ruthenium(II) octa-{beta}-halotetrakis(pentafluorophenyl)porphyrins (RuTFPPX{sub 8}(CO), RuTFPPCl{sub 8}(py){sub 2}; X = Cl, Br) have been synthesized, and the crystal structure of RuTFPPCl{sub 8}(CO)H{sub 2}O has been determined: C{sub 57}H{sub 28}Cl{sub 8}F{sub 20}N{sub 4}O{sub 5}-Ru, monoclinic, space group P2{sub 1}/c, a = 14.364(3) {angstrom}, b = 16.012(4) {angstrom}, c = 26.679(8){angstrom}, {beta} = 90.29(2){degree}, V = 6136(3) {angstrom}{sup 3}, Z = 4, R{sub w} = 0.028 on F{sup 2} for 8005 reflections, R{sub F} = 0.067 for 5378 reflections with F{sub o}{sup 2} > 3{sigma}(F{sub o}{sup 2}); the porphyrin is highly distorted, with 0.68 and 1.11 {angstrom} average displacements of the {beta}-chlorine atoms from the mean porphyrin plane. The reduction potentials of RuTFPPX{sub 8} complexes are much more positive (> 0.5 V) than those of unhalogenated analogues, owing to the influence of the electron-withdrawing X atoms. The relatively high energies of the Soret bands in the RuTFPPX{sub 8} electronic spectra are consistent with an electronic structural model involving Ru{sup II} back-bonding to the porphyrin e{pi}* orbitals.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 401815
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 7 Vol. 34; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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