Organometallics
Note
Chemical Industry, 0.911 M in THF, 4.0 mL) that contained NaBH4
(f) Hull, J. F.; Himeda, Y.; Wang, W. H.; Hashiguchi, B.; Periana, R.;
Szalda, D. J.; Muckerman, J. T.; Fujita, E. Nat. Chem. 2012, 4, 383.
(g) Kang, P.; Cheng, C.; Chen, Z. F.; Schauer, C. K.; Meyer, T. J.;
Brookhart, M. J. Am. Chem. Soc. 2012, 134, 5500. (h) Motokura, K.;
Kashiwame, D.; Miyaji, A.; Baba, T. Org. Lett. 2012, 14, 2642.
(
1
0.5 mol %) as a stabilizing reagent. After the THF solution was stirred
2 h, 13C{ H} and B{ H} NMR spectra of the solution were
1
11
1
recorded. The yield of (MeOBO) was 87%, which was determined
3
with the GC analysis of MeOH formed by hydrolysis of (MeOBO) .
3
1
3
1
11
1
C{ H} NMR (75.6 MHz, 297 K, THF): δ 51.6 (s). B{ H} NMR
(3) (a) Huang, F.; Zhang, C. G.; Jiang, J. L.; Wang, Z. X.; Guan, H. R.
(
96.4 MHz, 297 K, THF): δ 19.2 (s).
Monitoring the Reaction of Commercial BH ·THF. Under an
Inorg. Chem. 2011, 50, 3816. (b) Huff, C. A.; Sanford, M. S. J. Am.
Chem. Soc. 2011, 133, 18122. (c) Bontemps, S.; Vendier, L.; Sabo-
Etienne, S. Angew. Chem., Int. Ed. 2012, 51, 1671. (d) Mitton, S. J.;
Turculet, L. Chem.Eur. J. 2012, 18, 15258. (e) Park, S.; Bezier, D.;
Brookhart, M. J. Am. Chem. Soc. 2012, 134, 11404. (f) Sgro, M. J.;
Stephan, D. W. Angew. Chem., Int. Ed. 2012, 51, 11343.
3
atmosphere of CO , an NMR tube was charged with commercial BH ·
THF (Tokyo Chemical Industry, 0.911 M in THF, 0.5 mL), and then
2
3
a sealed capillary containing BCl was placed in the NMR tube to
3
calibrate the chemical shifts of the spectra for 2 days.
Reaction of Purified BH ·THF. Under an atmosphere of dry CO ,
3
2
(g) Wesselbaum, S.; vom Stein, T.; Klankermayer, J.; Leitner, W.
a Schlenk tube was charged with BH ·THF (0.993 M in THF, 2.8
3
Angew. Chem., Int. Ed. 2012, 51, 7499. (h) Berkefeld, A.; Piers, W. E.;
Parvez, M.; Castro, L.; Maron, L.; Eisenstein, O. Chem. Sci. 2013, 4,
mL), which was purified by trap-to-trap transfer. After the THF
solution was stirred 12 h, an 11B{ H} NMR spectrum of the solution
1
2
152. (i) Chakraborty, S.; Zhang, J.; Patel, Y. J.; Krause, J. A.; Guan, H.
was recorded, showing a signal at −0.5 ppm assigned to BH ·THF.
3
R. Inorg. Chem. 2013, 52, 37. (j) Bontemps, S.; Vendier, L.; Sabo-
Etienne, S. J. Am. Chem. Soc. 2014, 136, 4419.
Reaction of Purified BH ·THF in the Presence of NaBH .
3
4
Under an atmosphere of dry CO , a Schlenk tube was charged with
2
(4) (a) Ashley, A. E.; Thompson, A. L.; O’Hare, D. Angew. Chem., Int.
NaBH (1.52 mg) and BH ·THF (0.893 M in THF, 4.5 mL), which
4
3
Ed. 2009, 48, 9839. (b) Riduan, S. N.; Zhang, Y.; Ying, J. Y. Angew.
Chem,. Int. Ed. 2009, 48, 3322. (c) Huang, F.; Lu, G.; Zhao, L. L.; Li,
H. X.; Wang, Z. X. J. Am. Chem. Soc. 2010, 132, 12388. (d) Roy, L.;
Zimmerman, P. M.; Paul, A. Chem.Eur. J. 2011, 17, 435.
was purified by trap-to-trap transfer. After the THF solution was
stirred 12 h, (MeOBO) was obtained in 83% yield.
3
Reaction of Purified BH ·THF in the Presence of HCOONa.
3
Under an atmosphere of dry CO , a Schlenk tube was charged with
2
(e) Courtemanche, M.-A.; Larouche, J.; Legare, M.-A.; Bi, W.;
HCOONa (3.24 mg) and BH ·THF (0.893 M in THF, 5.34 mL),
3
Maron, L.; Fontaine, F.-G. Organometallics 2013, 32, 6804. (f) Menard,
G.; Stephan, D. W. Dalton Trans. 2013, 42, 5447. (g) LeBlanc, F. A.;
Piers, W. E.; Parvez, M. Angew. Chem., Int. Ed. 2014, 53, 789.
(h) Kwon, H. J.; Kim, H. W.; Rhee, Y. M. Chem.Eur. J. 2011, 17,
6501. (i) Binding, S. C.; Zaher, H.; Chadwick, F. M.; O’Hare, D.
Dalton Trans. 2012, 41, 9061. (j) Barry, B. M.; Dickie, D. A.; Murphy,
L. J.; Clyburne, J. A. C.; Kemp, R. A. Inorg. Chem. 2013, 52, 8312.
(k) Lu, Z.; Wang, Y.; Liu, J.; Lin, Y.-J.; Li, Z. H.; Wang, H.
Organometallics 2013, 32, 6753. (l) Das Neves Gomes, C.; Blondiaux,
E.; Thuery, P.; Cantat, T. Chem.Eur. J. 2014, 20, 7098.
which was purified by trap-to-trap transfer. After the THF solution was
stirred 12 h, (MeOBO) was obtained in 79% yield.
3
13
Reaction of Commercial BH ·THF with CO . Under an
atmosphere of N , an NMR tube with a J Young valve was charged
3
2
2
with commercial BH ·THF (Tokyo Chemical Industry, 0.911 M in
3
13
THF, 0.5 mL), and then the headspace gas was replaced with CO .
2
C
After 2.5 h, a 13C NMR spectrum of the solution was recorded. 13
NMR (75.6 MHz, 297 K, THF): δ 26.3 (t, THF), 51.6 (q,
(
MeOBO) ), 68.3 (t, THF), 125.8 (s, CO ).
3
2
ASSOCIATED CONTENT
Supporting Information
(5) Courtemanche, M.-A.; Legare, M.-A.; Maron, L.; Fontaine, F.-G.
J. Am. Chem. Soc. 2013, 135, 9326.
■
*
S
(
6) Recently, the reaction of BH ·SMe with CO in the presence of
3 2 2
Additional experimental data details including NMR data. This
strong bases was reported. Legare, M.-A.; Courtemanche, M.-A.;
Fontaine, F.-G. Chem. Commun. 2014, 50, 11362.
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AUTHOR INFORMATION
Notes
■
*
The authors declare no competing financial interest.
(9) (a) Buerchner, M.; Erle, A. M. T.; Scherer, H.; Krossing, I.
Chem.−Eur. J. 2012, 18, 2254. (b) Godfroid, R. A.; Hill, T. G.; Onak,
T. P.; Shore, S. G. J. Am. Chem. Soc. 1994, 116, 12107. (c) Hill, T. G.;
Godfroid, R. A.; White, J. P., III; Shore, S. G. Inorg. Chem. 1991, 30,
ACKNOWLEDGMENTS
■
This work was supported by Grants-in-Aid for Scientific
Research No. 25105741 from the Ministry of Education,
Culture, Sports, Science and Technology of Japan.
2
952.
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(
b) Wrackmeyer, B. Z. Naturforsch., B: Chem. Sci. 2004, 59, 1192.
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dx.doi.org/10.1021/om5008488 | Organometallics XXXX, XXX, XXX−XXX