TY - JOUR
T1 - Through-space interaction mediated by a sulfoxide
AU - Joel Meyer, G.
AU - Smith, Elliott R.
AU - Sakamoto, Takahiro
AU - Lichtenberger, Dennis L.
AU - Glass, Richard S.
N1 - Funding Information:
The authors gratefully acknowledge financial support of this work by the US National Science Foundation (Grant No. 0956581).
Publisher Copyright:
Copyright © 2015 Taylor & Francis Group, LLC.
PY - 2015/8/3
Y1 - 2015/8/3
N2 - Two new bisferrocenylphenylsulfoxides were synthesized and studied to determine the effect of the polar sulfoxide bond on through-space interaction between ferrocene moieties. The electronic and redox properties of these compounds were studied by ultraviolet (UV) photoelectron spectroscopy, cyclic voltammetry, differential pulse voltammetry, and density functional theory computations. Electrochemical results for 2,6-bis(ferrocenyl) thioanisole S-oxide 5b show two, fully reversible one-electron redox processes. The initial oxidation shows a 62-mV negative shift compared with the sulfide analog 2,6-bis(ferrocenyl)thioanisole, and an increased peak separation for the oxidation of 160 versus 145 mV. No peak separation is observed in 6b. No intervalence charge transfer band was observed in the complex 5b+1 by UV-Visible/Near-Infrared spectroscopy, ruling out electronic communication. Thus, the through-space electrostatic interactions of the sulfoxide renders the non-equivalent ferrocenes in 5b to have different oxidation potentials.
AB - Two new bisferrocenylphenylsulfoxides were synthesized and studied to determine the effect of the polar sulfoxide bond on through-space interaction between ferrocene moieties. The electronic and redox properties of these compounds were studied by ultraviolet (UV) photoelectron spectroscopy, cyclic voltammetry, differential pulse voltammetry, and density functional theory computations. Electrochemical results for 2,6-bis(ferrocenyl) thioanisole S-oxide 5b show two, fully reversible one-electron redox processes. The initial oxidation shows a 62-mV negative shift compared with the sulfide analog 2,6-bis(ferrocenyl)thioanisole, and an increased peak separation for the oxidation of 160 versus 145 mV. No peak separation is observed in 6b. No intervalence charge transfer band was observed in the complex 5b+1 by UV-Visible/Near-Infrared spectroscopy, ruling out electronic communication. Thus, the through-space electrostatic interactions of the sulfoxide renders the non-equivalent ferrocenes in 5b to have different oxidation potentials.
KW - Ferrocene
KW - electrostatic interaction
KW - mixed valence
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U2 - 10.1080/10426507.2014.991822
DO - 10.1080/10426507.2014.991822
M3 - Article
AN - SCOPUS:84938629396
VL - 190
SP - 1242
EP - 1246
JO - Phosphorus, Sulfur and Silicon and the Related Elements
JF - Phosphorus, Sulfur and Silicon and the Related Elements
SN - 1042-6507
IS - 8
ER -