Inorganic Chemistry
Article
mmol) was prepared in MeOH (10 mL). The resulting deep purple
mixture was stirred and heated at 50 °C for 4 h. After cooling to room
temperature, the reaction solution was treated with a solution of
Catalysis Experiments. A Young’s NMR tube was charged with 1
mmol of olefin, 1 mmol of silane or borane, 0.001 mmol of precatalyst,
0.4 mL of d -THF, and two drops of the integration standard
8
1
NaBPh in MeOH (10 mL), leading to precipitation of a blue solid.
mesitylene. The H NMR spectrum was recorded on the resulting
slurry (colorless solution) to establish the ratio of the standard to
4
This solid was collected by filtration and washed with MeOH (2 × 2
Me
mL) and Et O (2 × 3 mL) to afford [Fe(PN py) ](BPh ) . Yield:
reactants. The solution was treated with 2.5 mmol of 1 M NaBEt H in
3
2
2
4 2
1
1
5% (93 mg). H NMR (CD Cl ): δ 7.83 (m, 4H), 7.73 (m, 2H), 7.70
toluene (2.5 μL). The addition gives a homogeneous brown solution
2
2
(
6
(
5
m, 2H), 7.41 (m, 2H), 7.35 (m, 16H), 7.21 (m, 2H), 7.16 (m, 4H),
.98 (m, 16H), 6.90 (m, 4H), 6.87−6.80 (m, 12H), 6.63 (m, 2H), 6.56
m, 4H), 6.32 (m, 4H), 2.64 (s, 6H), 1.55 (br, 2H); *a resonance at
.33, assigned to CH Cl , was observed even after extended drying
(the dissolution process is noticeably exothermic for active catalysts).
1
The tube was shaken to mix all reagents, and H NMR spectra were
recorded at regular intervals to monitor the rate and nature of
products.
2
2
31
under vacuum. P NMR (CD Cl ): δ 60.7 (s, 2P). Anal. Calcd
2
2
(
found) for FeP N B C H ·CH Cl : C, 77.15 (77.21); H, 5.65
ASSOCIATED CONTENT
2
4
2
98 82
2
2
■
(
5.50); N, 4.24 (4.64).
*
S
Supporting Information
Ph
FeBr (PN py). A suspension of FeBr (80 mg, 0.37 mmol) in
1
H and 31P NMR spectra for new compounds. X-ray
2
2
Ph
THF (3 mL) was treated with a THF solution of PN py (156 mg,
.37 mmol), causing a color change from yellow to blue-green. The
0
mixture was stirred for 3 h, leading to a precipitation of a blue-green
solid. Pentane (10 mL) was added to the suspension while stirring to
further precipitate the blue-green solid. This solid was collected by
filtration, washed with pentane (2 × 5 mL), and dried to give
AUTHOR INFORMATION
■
Ph
1
FeBr (PN py) as a green powder. Yield: 89% (210 mg). H NMR
2
(
CD Cl ): δ 178, 75.7, 67.3, 17.8, 14.6, 13.9, 13.4, 7.71, 7.49, 5.62,
2 2
0
.18, −1.66, −3.72; *a resonance at 5.33, assigned to CH Cl , was
2
2
Author Contributions
observed even after extended drying under vacuum. Anal. Calcd
‡
R. Gilbert-Wilson and W.-Y. Chu contributed equally to this
(
found) for C H Br FeN P·0.5(CH Cl ): C, 52.29 (52.08); H, 3.45
30 23 2 2 2 2
work.
Notes
(
3.36); N, 4.00 (4.20).
Ph
Fe(PN py)(CO) . An Et O suspension (ca. 30 mL) containing
2
2
Ph
FeBr (PN py) (43 mg, 0.065 mmol) was saturated with CO. A
The authors declare no competing financial interest.
2
toluene solution of NaBEt H (1 M, 130 μL, 0.13 mmol) was diluted
3
with Et O (ca. 5 mL) and transferred via cannula into the
2
ACKNOWLEDGMENTS
This research was conducted under contract DEFG02-
0ER14146 with the U.S. Department of Energy by its
Division of Chemical Sciences, Office of Basic Energy Sciences.
We thank Drs. Danielle Gray and Jeffrey Bertke for assistance
with the X-ray crystallography.
Ph
■
9
FeBr (PN py) suspension under positive CO pressure. The solution
2
gradually darkened to give a green mixture. After stirring under CO for
1
6 h, the solution was filtered with Celite and dried under reduced
pressure. The resulting green powder was recrystallized by layering
pentane over a concentrated Et O solution, yielding the target
2
compound as dark green crystals. Yield: 28 mg (77%). Single crystals
1
suitable for X-ray diffraction were also obtained this way. H NMR
(
4
6
CD Cl ): δ 9.39 (dd, 6.4, 1.4 Hz, 1H), 7.54 (ddd, 11.3, 8.2, 1.5 Hz,
REFERENCES
2
2
■
H), 7.49−7.25 (m, 12H), 7.09−7.03 (m, 2H), 7.00−6.95 (m, 1H),
(
1) Peoples, B. C.; Rojas, R. S. In Olefin Upgrading Catalysis by
Nitrogen-Based Metal Complexes II; Giambastiani, G., Cam
31
.90 (ddd, 8.5, 6.5, 1.4 Hz, 1H), 6.65−6.52 (m, 2H). P NMR
́
pora, J.,
−1
(
CD Cl ): δ 78.1 (s, 1P). IR (CH Cl ): 1949, 1890 cm . Anal. Calcd
2 2 2 2
Eds.; Springer: Berlin, 2011; pp 39−75;. Gibson, V. C.; Redshaw, C.;
for C H FeN O P·0.5Et O (found): C, 69.05 (69.1); H, 4.77 (4.90);
N, 4.74 (4.94).
32
23
2
2
2
Solan, G. A. Chem. Rev. 2007, 107, 1745−1776.
(
2) Peng, D.; Zhang, Y.; Du, X.; Zhang, L.; Leng, X.; Walter, M. D.;
Ph
Ph
PNH py. To a toluene solution (3 mL) of PN py (139 mg, 0.31
Huang, Z. J. Am. Chem. Soc. 2013, 135, 19154−19166.
(3) Chirik, P. J. In Catalysis without Precious Metals; Bullock, R. M.,
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mmol) was added a 1 M toluene solution of NaBEt H (320 μL, 0.32
3
mmol). The originally yellow solution gradually darkens, and bright
yellow precipitates start forming after ca. 5 min. After stirring for an
additional 3 h, the mixture was added to pentane (15 mL) and filtered.
The bright yellow precipitate was then dissolved in MeOH (10 mL) to
form a colorless solution. The solution was concentrated to ca. 2 mL
and stored at −10 °C for 16 h to yield the target compound as a solid
white precipitate. Yield: 98 mg (70%). H NMR (CDCl ): δ 8.51
(
7
(
4) Knijnenburg, Q.; Gambarotta, S.; Budzelaar, P. H. M. Dalton
Trans. 2006, 5442−5448.
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(
2
(
1
3
2013, 52, 3676−3680. Zhang, L.; Zuo, Z.; Leng, X.; Huang, Z. Angew.
Chem., Int. Ed. 2014, 53, 2696−2700. Gunanathan, C.; Milstein, D.
Acc. Chem. Res. 2011, 44, 588−602.
ddd, J = 4.9, 1.8, 0.9 Hz, 1H), 7.51 (td, J = 7.7, 1.8 Hz, 1H), 7.44−
.32 (m, 10H), 7.23−7.15 (m, 5H), 7.13−7.06 (m, 3H), 6.81 (ddd, J =
.6, 6.0, 1.6 Hz, 1H), 6.60 (t, J = 7.4 Hz, 1H), 6.51−6.46 (m, 1H), 6.15
7
(
7) DuBois, T. D. Inorg. Chem. 1972, 11, 718−722. DuBois, T. D.;
31
(
br, 1H), 5.64−5.58 (m, 1H). P NMR (CDCl ): δ − 18.8 (s, 1P).
3
Smith, F. T. Inorg. Chem. 1973, 12, 735−740.
Anal. Calcd for C H N P (found): C, 81.06 (80.64); H, 5.67 (5.65);
30
25
2
(8) Ben-Daat, H.; Hall, G. B.; Groy, T. L.; Trovitch, R. J. Eur. J. Inorg.
Chem. 2013, 2013, 4430−4442. Mukhopadhyay, T. K.; Flores, M.;
Groy, T. L.; Trovitch, R. J. J. Am. Chem. Soc. 2014, 136, 882−885.
N, 6.30 (6.38).
Ph
FeBr (PNH py). A suspension of FeBr (48 mg, 0.22 mmol) in
2
2
Ph
THF (3 mL) was treated with a THF solution of PNH py (92 mg,
.22 mmol). After stirring for ca. 1 min, a bright yellow solid
(
9) Porter, T. M.; Hall, G. B.; Groy, T. L.; Trovitch, R. J. Dalton
Trans. 2013, 42, 14689−14692.
0
precipitate formed. The mixture was stirred for an additional 3 h,
followed by addition of pentane (10 mL). The bright yellow solid was
collected by filtration, washed with pentane (2 × 5 mL), and dried to
(10) Schmiege, B. M.; Carney, M. J.; Small, B. L.; Gerlach, D. L.;
Halfen, J. A. Dalton Trans. 2007, 2547−2562. Small, B. L.; Rios, R.;
Fernandez, E. R.; Carney, M. J. Organometallics 2007, 26, 1744−1749.
Small, B. L.; Rios, R.; Fernandez, E. R.; Gerlach, D. L.; Halfen, J. A.;
Carney, M. J. Organometallics 2010, 29, 6723−6731.
(11) Cooper, M. K.; Downes, J. M.; Duckworth, P. A. Inorg. Synth.
1989, 29, 129−133.
Ph
give FeBr (PNH py) as a bright yellow powder. Yield: 93% (141 mg).
2
1
H NMR (CD Cl ): δ 95.2, 52.9, 46.1, 17.3, 15.8, 13.7, 11.2, 10.2, 9.6,
2
2
8
0
.3, 4.9, 3.8, 2.1, −1.7, −3.9, −52.27. Anal. Calcd for C H Br FeN P·
30
25
2
2
.5H O (found): C, 53.85 (53.61); H, 3.92 (3.73); N, 4.19 (4.36).
2
G
Inorg. Chem. XXXX, XXX, XXX−XXX