1
00
E. Erasmus / Inorganica Chimica Acta 378 (2011) 95–101
3
.2.6. 1,3-Diruthenocenyl-2-propen-1-one (8)
Yield 20% (24 mg). R = 0.48 (Hexane:ether, 1:1). d
CDCl )/ppm: 4.55 (s; 5H; C ); 4.59 (s; 5H; C ); 4.74 (t; 2H;
); 4.85 (t; 2H; C ); 4.94 (t; 2H; C ); 5.16 (t; 2H; C );
.54 (d; 1H; CH); 7.49 (d; 1H; CH). Microanalysis calculated C
3.7%, H 3.9% and found C 53.3%, H 4.0%.
References
f
H
(300 MHz,
[
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H
5 5
5 5
H
(
(
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C
6
5
H
5 4
5
H
4
5
H
4
5 4
H
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(
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.2.7. 3-Phenyl-1-ruthenocenyl-2-propen-1-one (4)
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(
f
H
(300 MHz,
(
3
5
H
5
5 4
H
[
[
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C
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H
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6
H
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6 5
H
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(
(
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3.3. Electrochemistry
(
2
b) M.D. Maree, E.W. Neuse, E. Erasmus, J.C. Swarts, Metal Based Drugs (2008)
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ꢀ3
(c) J.C. Swarts, T.G. Vosloo, S.J. Cronje, W.C. du Plessis, C.E.J. van Rensburg, E.
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in dry air free acetonitrile (99.8%) containing 0.10 mmoldm tetra-
butylammonium hexafluorophosphate as supporting electrolyte
were conducted under a blanket of purified argon at 25 °C utilizing
a BAS 100 B/W electrochemical workstation interfaced with a per-
sonal computer. A three electrode cell, which utilized a Pt auxiliary
(
e) J.C. Swarts, D.M. Swarts, D.M. Maree, E.W. Neuse, C. La Madeleine, J.E. Van
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(
electrode,
a glassy carbon working electrode (surface area
2
+
ꢀ3
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0
3
.0707 cm ) and an Ag/Ag (0.010 moldm AgNO ) reference elec-
trode [29] mounted on a Luggin capillary [30,31] were employed.
Successive experiments under the same experimental conditions
showed that all formal reduction and oxidation potentials were
reproducible within 5 mV. Experimentally potentials were refer-
enced against a Ag/Ag+ reference electrode, but results are pre-
sented referenced against ferrocene as an internal standard. To
achieve this, each experiment was performed first in the absence
(
b) A. Aguilar-Aguilar, E. Peña-Cabrera, L.S. Liebeskind, Arkivoc (2004) 156.
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(
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ꢀ3
of ferrocene and then repeated in the presence of <1 mmoldm
ferrocene. Data were then manipulated on a spreadsheet to set
+
the formal reduction potentials of FcH/FcH couple at 0 V.
[
(
b) M.F.R. Fouda, M.M. Abd-Elzaher, R.A. Abdelsamaia, A.A. Labib, Appl.
4
. Conclusion
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[
This study has shown that ferrocenyl- and ruthenocenyl-con-
(
b) Y. Jung, K.I. Son, Y.E. Oh, D.Y. Noh, Polyhedron 27 (2008) 861;
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[
There exists a linear correlationbetween the sum of the R-group’s
P
1
2
group electronegativity (
v
R
=
v
R1
+
v
R2 for R COCH@CHR ) of the
[
metallocenes in compounds 5–8 and the carbonyl stretching fre-
quency. UV/Vis spectra of the compounds that contain a ferrocenyl
moiety displayed two absorption bands, while the compounds that
have only a ruthenocenyl moiety only showed one absorption band.
[
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(
(
b) W.C. du Plessis, W.L. Davis, S.J. Cronje, J.C. Swarts, Inorg. Chim. Acta 314
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All compounds revealed a chemically and electrochemically
[
[
[
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+
reversible Fc/Fc couple with
D
E ca. 80 mV and ipa/ipc = 0.98 ꢀ 0.85
and an irreversible Rc/Rc2 couple in CH
+
CN/0.1 moldm [NBu
ꢀ3
]
3
4
[
6
PF ]. It was found that the position of the metallocene in McC-
OCH@CHMc (closer to the carbonyl or the double bond) influences
the reduction potential of the electroactive metallocenyl moiety.
(
b) M.G. Hill, W.M. Lamanna, K.R. Mann, Inorg. Chem. 30 (1991) 4687.
[
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(
(
(
1997) 13;
Acknowledgement
b) M. Watanabe, I. Motoyama, T. Takayama, M. Sato, J. Organomet. Chem. 517
1996) 115;
The author would like to acknowledge the University of the Free
State for financial support.
(c) T.P. Smith, D.J. Iverson, M.W. Droege, K.S. Kwan, H. Taube, Inorg. Chem. 26
1987) 2882.
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(
[
[
24] J.C. Swarts, A. Nafady, J.H. Roudebush, S. Trupia, W.E. Geiger, Inorg. Chem. 48
(
2009) 2156.
Appendix A. Supplementary material
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