1358
K.E. Thiesen et al. / Journal of Organometallic Chemistry 696 (2011) 1355e1358
white solid in 20 mL of dry THF, was then transferred to the addition
funnel (via syringe) before being added dropwise to the reaction
mixture. The reactionwas allowed tocome toroomtemperature and
then stirred for an additional 20 h, at which point it was carefully
quenched with water and extracted with ether. The ether layer was
washedwith water(3 ꢁ 20 mL) and dried over Na2SO4, and the crude
ortho-mercurated ferrocenyl-acetal (2) was purified by flash chro-
matography (silica, 4:1 hexanes/EtOAc). Deprotection of 2 was
accomplished as follows: the dark red oil (2.66 g, 4.83 mmol) in
dichloromethane (70 mL) was added to a 250 round-bottomed flask,
followed by the addition of DI water (30 mL) and 2.0 g of PTSA
(p-toluenesulfonic acid monohydrate,10.5 mmol), and the resulting
mixture was stirred for 24 h. The crude product (Sp-3) was extracted
with CH2Cl2 and washed with water (3 ꢁ 20 mL), and the organic
layer was dried over Na2SO4 before the solvent was removed under
reduced pressure. Further purification of Sp-3 may be accomplished
by small batch flash chromatography (silica, 4:1 hexanes:EtOAc) or
via re-crystallization (by layering a CH2Cl2 solution of Sp-3 with
placed in the N2(g) cold stream provided by a CryoIndustries
apparatus. Data collection was carried out with the use of SMART
software, and data reduction was done using SAINT and corrected
for absorption using SADABS [19]. The structure was solved with
the use of SHELXS97 and refined with SHELXL97 [20]. Hydrogen
atoms were added geometrically and refined with a riding model.
4.5. CD spectroscopy
Samples analyzed via CD spectroscopy (Fig. 2) were prepared in
CH2Cl2: (Sp)-3; c ¼ 2 mM, (Sp,Sp,Rc,Rc)-5; c ¼ 2 mM. The same
samples were also used to obtain UVeVis spectra for these two
compounds.
Acknowledgment
We would like to acknowledge the following individuals for
their help during this project: (a) Dr. Krish Krishnan (Department of
Chemistry, CSU Fresno) for providing us with access to the CD
spectropolarimeter in the RIMI lab at CSU Fresno (funded by NIH
grant # 5P20MD002732); (b) Dr. James Miranda (Department of
Chemistry, CSU Sacramento) for collecting the NMR data; (c) Mr.
Douglas Kliewer (Department of Chemistry, CSU Fresno) for his
help with the operation and maintenance of the analytical instru-
ments in our department; (d) Dr. Andrew Rogerson (Dean, College
of Science and Math, CSU Fresno) for partial financial support of this
research through a Faculty-Sponsored Student Research award.
hexanes). mp 144e145 ꢀC.1H NMR(CDCl3),
d: 4.32 (s, 5H, C5H5); 4.62
(m,1H, C5H3); 4.82 (m,1H, C5H3); 4.94(m,1H, C5H3);10.13 (d,1H, CH]
O, JHgeH ¼ 0.96 Hz). 13C{1H}-NMR(CDCl3),
d: 70.35 (C5H5); 73.59
(C5H3, CH); 75.92 (C5H3, CH); 78.80 (C5H3, CH); 81.94 (C5H3, C-HgCl);
83.48 (C5H3, C-CHO); 193.84 (CH]O). IR; v(cmꢂ1): 3094 (w), 2844
(w), 1648 (C]O, s), 1430 (m), 1409 (m), 1361 (m), 1349 (m), 1327 (w),
1225 (m), 1106 (m), 1032 (m), 1001 (m), 827 (m), 755 (m), 734 (m).
4.3. (Sp,Sp,Rc,Rc)-N,N-bis(2-(chloromercurio)ferrocenylidene)-1,2-
diphenylethane-1,2-diimine, (Sp,Sp,Rc,Rc)-5
To a 10 mL round-bottomed flask were added (Sp)-3 (0.050 g,
0.11 mmol), (R,R)-4 (0.0118 g, 0.055 mmol), and 5 mL of dry toluene.
Activated alumina (0.1 g) was also added to the flask, and the
mixture was heated to 50 ꢀC and stirred at that temperature for
24 h. The reaction mixture was then filtered through celite before
the solvent was removed under reduced pressure, leaving a crude
red oil which was allowed to dry further under high vacuum. Re-
crystallization was accomplished by dissolving the crude product in
a minimum of CH2Cl2 and layering this solution with hexanes. The
resulting crystalline product, (Sp,Sp,Rc,Rc)-5, was harvested and
Appendix. Supplementary data
Supplementary data related to this article can be found online at
X-ray crystallograpic data for (Sp,Sp,Rc,Rc)-5 is available in CIF
format.
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Crystals suitable for single-crystal X-ray diffraction analysis
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layered with hexanes; orange plate (0.26 ꢁ 0.17 ꢁ 0.10 mm3).
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