Please use this identifier to cite or link to this item:
|Title:||Highly oxidized ruthenium organometallic compounds. The synthesis and one-electron electrochemical oxidation of [Cp*RuIVCl 2(S2CR)] (Cp* = η5-C 5Me5, R = NMe2, NEt2, O iPr)|
|Authors:||Kuan, S.L. |
|Citation:||Kuan, S.L., Tay, E.P.L., Leong, W.K., Goh, L.Y., Lin, C.Y., Gill, P.M.W., Webster, R.D. (2006-12-18). Highly oxidized ruthenium organometallic compounds. The synthesis and one-electron electrochemical oxidation of [Cp*RuIVCl 2(S2CR)] (Cp* = η5-C 5Me5, R = NMe2, NEt2, O iPr). Organometallics 25 (26) : 6134-6141. ScholarBank@NUS Repository. https://doi.org/10.1021/om060866z|
|Abstract:||[Cp*RuIVCl2(S2CR)] (R = NMe 2, NEt2, OiPr) were synthesized by the reaction of [Cp*RuIIICl2]2 with [RC(S)S] 2. One-electron electrochemical oxidation of [Cp*RuCl 2(S2CR)] produces paramagnetic [Cp*RuCl 2(S2CR)]+, which are stable in CH 2Cl2 solution for at least several hours at 233 K. EPR experiments performed at 293 K show isotropic signals (g ≈ 2.035) with clearly defined hyperfine coupling to 99Ru and 101Ru of 25 G and with peak-to-peak line widths of 15 G. At temperatures below 153 K, axial-shaped EPR spectra were obtained with g-values close to 2 (2.050-2.008) and narrow peak-to-peak line widths (15 G). Results from DFT calculations indicate that approximately 70% of the spin density in [Cp*RuCl 2(S2CNMe2)]+ is located on the ruthenium, although there is an increase of only 0.06 in the positive charge of the metal ion as a result of the oxidation. The high spin density on Ru supports the assignment of a formally Ru(V) oxidation state, which is unprecedented in organometallic chemistry. Chemical oxidation of Cp*RuIVCl 2(S2CNMe2) with NO(PF6) in CH 3CN resulted in the isolation of [Cp*RuIV(MeCN) 2(S2CNMe2)]+2 (4), while oxidation with [(4-Br-C6H4)3N](SbCl6) in CH2Cl2 resulted in the formation of chloro-bridged dimeric [Cp*RuIVCl(S2CNMe2)]2 +2 (5). When 5 is dissolved in CD3-CN/CH3CN, it immediately converts to 4. Cyclic voltammetric experiments confirmed that in both solvents the chemical oxidation process occurred through the [Cp*RuvCl2(S2CNMe2)] + intermediate. © 2006 American Chemical Society.|
|Appears in Collections:||Staff Publications|
Show full item record
Files in This Item:
There are no files associated with this item.
checked on Mar 19, 2019
WEB OF SCIENCETM
checked on Mar 19, 2019
checked on Mar 9, 2019
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.