Oxidation of Cymantrene Analogues of Ferrocifen: Electrochemical, Spectroscopic, and Computational Studies of the Parent Complex 1,1′-Diphenyl-2-cymantrenylbutene

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Title
Oxidation of Cymantrene Analogues of Ferrocifen: Electrochemical, Spectroscopic, and Computational Studies of the Parent Complex 1,1′-Diphenyl-2-cymantrenylbutene
Author(s)
Kan Wu; Ji Young Park; Rachael Al-Saadon; Hyerim Nam; Yujin Lee; Siden Top; Gerard Jaouen; Mu-Hyun Baik; William E. Geiger
Publication Date
2018-06
Journal
ORGANOMETALLICS, v.37, no.12, pp.1910 - 1918
Publisher
AMER CHEMICAL SOC
Abstract
The oxidative electrochemical behavior of 1,1′-diphenyl-2-cymantrenylbutene (1), a cymantrene analogue of the breast cancer drug ferrocifen, was shown to involve the sequential electron-transfer series 1/1+/12+ in dichloromethane/0.05 M [NBu4][B(C6F5)4] (E1/2 values 0.78 and 1.18 V vs ferrocene). By a combination of spectroscopic and computational techniques, it was shown that the cymantrene functionality plays an important role in dissipating the positive charges in the oxidized compounds and is therefore an active participant in the redox events. The redox-active orbital goes from roughly equal degrees of organometallic and π-organic (diphenylolefin) makeup in 1 to increasingly organic based fractions in 1+ and 12+. Structural changes mimicking those of oxidized tetrakis(aryl)ethylenes accompany the one-electron oxidations. There is sufficient unpaired electron density on the manganese center in 1+ to allow for oxidatively induced ligand exchange of one or more of the carbonyl ligands with donor ligands, including phosphites and pyridine. The complex Mn(CO)2P(OPh)3(η5-C5H4(Et)C=C(C6H5)2) was prepared by the electrochemical switch method, wherein [Mn(CO)2P(OPh)3(η5-C5H4(Et)C=C(C6H5)2)]+, produced by the oxidation of 1 in the presence of P(OPh)3, was reduced back to the neutral CO-substituted complex. © 2018 American Chemical Society
URI
https://pr.ibs.re.kr/handle/8788114/4971
ISSN
0276-7333
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
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