Organometallics
Article
solid was extracted with 15 mL of toluene and filtered through Celite
on a coarse frit. The toluene filtrate was transferred to a scintillation
vial. A 0.8559 g portion of Me3SiI (4.28 mmol, 1.73 equiv) was added
dropwise as a toluene solution (2 mL) at ambient temperature, and
the reaction mixture was allowed to stir for 1 h. At the end of the
reaction, 5 mL of THF was added to quench the extra Me3SiI. The
volatiles were removed under reduced pressure. The resulting yellow
solid was dissolved in a minimum amount of Et2O layered with n-
pentane. Yellow crystals as (NNfc)HoI(THF)2 formed after three days
of storing in a −35 °C freezer. Yield: 0.818 g. After decanting, the
mother liquor was concentrated and stored in a −35 °C freezer to give
a second crop: 0.351 g. Total yield: 1.169 g, 68.4% (based on
H2(NNfc), 54.7% based on Ho). 1H NMR (300 MHz, C6D6, 25 °C) δ,
ppm: 315.7 (br s, 12H, SiCH3), 199.6 (br s, 18H, C(CH3)3), −137.4
(br s), −142.5 (br s), and −223.6 (br s). Peaks were too broad to get
reasonable integrations and assign them. Anal. Calcd for
C30H54N2O2FeIHoSi2, Mw = 878.625, with 0.25 molecule of n-
pentane: C, 41.86; H, 6.41; N, 3.12. Found: C, 41.75; H, 6.34; N, 3.08.
Yields for the analogous Nd, Gd, and Er syntheses: first crop,
0.507 g; second crop, 0.195 g; total 0.702 g, 69.6% (Nd); first crop,
0.524 g; second crop, 0.279 g; total 60.7% (Gd); first crop, 0.664 g;
second crop, 0.165 g; total 61.9% (Er).
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C26H46N2OFeINdSi2, Mw = 785.830: C, 39.74; H, 5.90; N, 3.56.
Found: C, 40.21; H, 5.57; N, 4.01.
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Synthesis of (NNfc)HoI(THF)2 Using 3 equiv of KBn and 1
equiv of H2(NNfc). Scale: 0.800 g of HoCl3(THF)3.5 (1.53 mmol),
0.597 g of KBn (4.58 mmol), 0.679 g of H2(NNfc) (1.53 mmol), and
0.611 g of Me3SiI (3.05 mmol). The procedure was the same as using
2.4 equiv of KBn. Yield: first crop, 0.520 g; second crop, 0.380 g; total
67.0%.
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ASSOCIATED CONTENT
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S
* Supporting Information
Details of synthetic procedures, NMR spectra, and the X-ray
crystallographic study can be found online. This material is
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AUTHOR INFORMATION
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Corresponding Author
Author Contributions
W.H. and P.L.D. designed the experiments. W.H. performed all
the syntheses and NMR spectroscopy. B.M.U. performed the
elemental analysis. S.I.K. solved some molecular structures by
X-ray crystallography. W.H. and P.L.D. wrote the manuscript.
All authors have given approval to the final version of the
manuscript.
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L.; Liable-Sands, L. M.; Rheingold, A. L.; Markworth, P. R.; Chang, R.
P. H.; Chudzik, M. P.; Kannewurf, C. R.; Marks, T. J. Inorg. Chem.
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported by the U.S. Department of Energy,
Office of Basic Energy Sciences, Heavy Element Chemistry
Program under Grant No. ER15984.
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dx.doi.org/10.1021/om3010433 | Organometallics XXXX, XXX, XXX−XXX