Organometallics
Article
1
2
7.41; H, 2.79. Found: C, 27.98; H, 3.04. H NMR (C D , 400.13
Transfer Dehydrogenation Studies. A typical stock catalyst
6
6
+
CF
3
MHz, 20 °C): δ 9.91 (br s, 1H; HNEt ), 6.88 (m, 3H; overlapping m-
and p-C H (CH P(CF ) ) ), 4.13 (dt(pseudo), J = 17 Hz, JPH = 5
Hz, 2H; C H (CH P(CF ) ) ), 3.55 (dt(pseudo), J = 17 Hz, JPH
solution was prepared from 5 mg of ( PCP)Os(cod)H (6.8 μmol)
and 2.75 mL of cyclooctadiene (3,030 equiv). Then 250 μL of stock
solution and 240 μL of tert-butylethylene (3,030 equiv) were added to
3
2
6
3
2
3
2
2
HH
2
=
6
3
2
3
2
2
HH
4
Hz, 2H; C H (CH P(CF ) ) ), 2.24 (m, 6H; NCH CH ), 0.66 (t,
a 5 mm NMR tube fitted with a Teflon valve with an acetone-d
6
6
3
2
3
2
2
2
3
3
31
JHH = 7 Hz, 9H; NCH CH ). P{H} NMR (C D , 161.97 MHz, 20
capillary external lock and heated to the desired temperature in an oil
bath. NMR tubes were removed from the oil bath periodically and
allowed to cool to room temperature before collecting spectra. The
equivalents of cyclooctene produced were calculated by integration of
the vinylic cyclooctene resonance at δ 4.96 against the vinylic tert-
butylethylene resonance at δ 5.18.
2
3
6
6
°
6
C): δ 59.1 (m). 19F NMR (C D , 376.50 MHz, 20 °C): δ −51.2 (m,
6
6
−1
F; PCF ), −56.1 (m, 6F; PCF ). IR (CH Cl , cm ): ν(CO) = 1970.
3
3
2
2
CF CF −
3
3
cis-( PCP)Os(CO) Cl (2). cis-[( PCP)Os(CO)Cl ] [HN-
2
2
+
(
CH CH ) ] (0.300 g, 0.360 mmol) and TMSOTf (327 μL, 1.80
2 3 3
mmol) were added to toluene (∼25 mL) and stirred one week at room
temperature under one atmosphere of CO. The volatiles were
removed, and the residue was triturated with methanol to give a white
solid, which was collected by filtration and dried (0.060 g, 32% yield).
Crystals suitable for X-ray diffraction were grown by slow diffusion of
methanol into a benzene solution of 2. Anal. Calcd for OsP F C H :
C, 23.26; H, 0.98. Found: C, 23.15; H, 0.86. H NMR (C D , 400.13
MHz, 20 °C): δ 6.74 (br s, 1H; p-C H (CH P(CF ) ) ), 6.68 (br s,
2
Acceptorless Dehydrogenation Studies. A typical catalyst
CF
3
solution was prepared from 5 mg of ( PCP)Ru(cod)H (7.7 mol)
and 3.12 mL of cyclooctadiene (3030 equiv), and mesitylene (5.3 L, 5
equiv) was added as an internal standard. The solution was refluxed
under N for the desired time before cooling to room temperature and
2
2
12 10
7
1
withdrawing an aliquot for NMR analysis. The equivalents of
cyclooctene produced were calculated by integration of the product
vinylic cis- and trans-cyclodecene resonances at 4.46 and 4.52 ppm,
respectively, against the mesitylene aromatic resonance at 5.80 ppm
6
6
6
3
2
3 2 2
H; m-C H (CH P(CF ) ) ), 3.79 (m, 2H; C H (C(H)HP-
6 3 2 3 2 2 6 3
31
(
(
CF ) ) )), 3.24 (m, 2H; C H (C(H)HP(CF ) ) )). P{H} NMR
C D , 161.97 MHz, 20 °C): δ 59.3 (m). F NMR (C D , 376.50
3 2 2 6 3 3 2 2
19
(referenced to an acetone-d capillary external lock).
6
6
6
6
6
X-ray Crystallography. The X-ray diffraction data for all
complexes were measured at 150 K on a Bruker SMART APEX II
CCD area detector system equipped with a graphite monochromator
and a Mo Kα fine-focus sealed tube operated at 1.5 kW power (50 kV,
30 mA). Crystals were attached to glass fibers using Paratone N oil.
Collection and refinement details are included in the Supporting
Information.
MHz, 20 °C): δ −51.3 (m, 6F; PCF ), −58.0 (m, 6F; PCF ). IR
3
3
−1
(
CH Cl , cm ): ν(CO) 2073, 2006.
2 2
3
CF
cis-( PCP)Os(CO) H (3). Complex 3 was prepared on a small
2
CF
3
scale for NMR analysis: cis-( PCP)Os(CO) Cl (0.012 g, 0.017
mmol) and (Et Si) (μ-H) B(C F ) (0.017 g, 0.019 mmol) were
dissolved 0.5 mL of benzene-d and placed under 1 atm of CO. NMR
2
+
−
3
2
6 5 4
6
confirmed clean conversion of 2 to 3 after one hour. NMR data for 3:
1
H NMR (C D , 400.13 MHz, 20 °C): δ 6.84 (m, 1H; p-
6
6
ASSOCIATED CONTENT
C H (CH P(CF ) ) ), 6.69 (m, 2H; m-C H (CH P(CF ) ) ), 3.41
■
6
3
2
3
2
2
6
3
2
3 2 2
2
(
m, 2H; C H (C(H)HP(CF ) ) )), 3.29 (dm, J = 17 Hz, 2H;
S
6
3
3
2
2
HH
* Supporting Information
2
31
C H (C(H)HP(CF ) ) ), −8.11 (t, J = 24 Hz, 1H; OsH). P{H}
NMR (C D , 161.97 MHz, 20 °C): δ 65.0 (m). F NMR (C D ,
6
3
3
2
2
HP
Text and tables giving X-ray diffraction data collection and
refinement details and CIF files giving crystallographic data for
1
9
6
6
6
6
3
3
J
76.50 MHz, 20 °C): δ −61.0 (t, J = 38 Hz, 3F; PCF ), −62.4 (t,
FF
3
3
−1
= 43 Hz, 3F; PCF ). IR (CH Cl , cm ): ν(CO) = 2064, 2020.
3 2 2
FF
Crystals suitable for X-ray diffraction were grown by slow diffusion of
hexane to benzene.
CF
3
3
AUTHOR INFORMATION
(
PCP)Os(cod)H (4). Os(cod)(η -2-methylallyl) (0.200 g, 0.490
2
3
■
CF
mmol),
PCPH (137 μL, 0.216 g, 0.490 mmol), and 5 mL of
Notes
cyclooctadiene were placed in a heavy-walled reaction tube equipped
with a Teflon valve and charged with 3 atm of H . The mixture was
The authors declare no competing financial interest.
2
stirred vigorously at 130 °C for 24 h. Upon cooling, the solution was
transferred to a round-bottomed flask and pulled to dryness. The
residue was taken up in 15 mL of petroleum ether and stirred at room
temperature to give a yellow solution. Concentration to ∼2 mL and
filtration yielded 0.080 g (22% yield). Crystals suitable for X-ray
diffraction were grown from a benzene solution by slow evaporation.
Anal. Calcd for OsP F C H : C, 32.44; H, 2.72. Found: C, 32.56; H,
ACKNOWLEDGMENTS
■
We thank the National Science Foundation (CHE-0911739
and CHE-1213903), DOE/EPSCoR (DE-FG02-08ER15979),
and the Wyoming School of Energy Resources for financial
support.
2
12 20 20
2
.86. 1H NMR (C D , 400.13 MHz, 20 °C): δ 6.75 (m, 3H;
6 6
REFERENCES
C H (CH P(CF ) ) ), 4.19 (br s, 2H; vinylic cod CH), 3.76 (m, 2H;
6
3
2
3
2
2
■
2
C H (C(H)HP(CF ) ) )), 3.25 (dm, J = 17 Hz, 2H; C H (C(H)
6
3
3
2
2
HH
6
3
(1) Choi, J.; MacArthur, A. H. R.; Brookhart, M.; Goldman, A. S.
Chem. Rev. 2011, 111, 1761.
(2) Haibach, M. C.; Kundu, S.; Brookhart, M.; Goldman, A. S. Acc.
HP(CF ) ) )), 2.61 (br s, 2H; vinylic cod CH), 2.25 (m, 4H; cod
3
2 2
2
3
2
CH ), 1.82 (dd, J ≈ J ≈ 17 Hz, 4H; cod CH ), −12.65 (t, J
2
HH
HH
2
HP
3
1
=
6
29 Hz, 1H; OsH). P{H} NMR (C D , 161.97 MHz, 20 °C): δ
6 6
Chem. Res. 2012, 45, 947.
7.6 (m). 19F NMR (C D , 376.50 MHz, 20 °C): δ −56.6 (m, 6F;
6
6
(3) (a) Wei, Y.; Xue, D.; Lei, Q.; Wang, C.; Xiao, J. Green Chem.
2013, 15, 629. (b) Polukeev, A. V.; Petrovskii, P. V.; Peregudov, A. S.;
Ezernitskaya, M. G.; Koridze, A. A. Organometallics 2013, 32, 1000.
(c) Leitch, D. C.; Lam, Y. C.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem.
Soc. 2013, 135, 10302. (d) Wetherby, A. E.; Mucha, N. T.; Waterman,
R. ACS Catal. 2012, 2, 1404. (e) Brueck, A.; Gallego, D.; Wang, W.;
Irran, E.; Driess, M.; Hartwig, J. F. Angew. Chem., Int. Ed. 2012, 51,
11478.
(4) Adams, J. J.; Arulsamy, N.; Roddick, D. M. Organometallics 2012,
31, 1439.
(5) Roddick, D. M. Top. Organomet. Chem. 2013, 40, 49.
(6) Gruver, B. C.; Adams, J. J.; Warner, S. J.; Arulsamy, N.; Roddick,
D. M. Organometallics 2011, 30, 5133.
PCF ), −64.3 (m, 6F; PCF ).
3
3
CF
3
6
3 CF
3
(
μ PCPH)Os(H)(μ-H)(μ,η ,κ - PCP)Os(H) (5). A 5 mm NMR
tube fitted with a Teflon valve was charged with 5 mg of 4, 0.5 mL of
benzene-d , and 3 atm of H . Warming to 130 °C for 48 h resulted in a
6
2
3
1
solution with 5 as the major species (∼55%) as determined by
NMR. Solutions of 5 can be alternatively prepared by thermolysis of 4
in cyclodecane at 200 °C for one hour. Partial spectroscopic data for 5:
P
1
2
H NMR (C D , 400.13 MHz, 20 °C): δ −13.36 (ps q, J = 25 Hz,
6
6
HP
2
1
H; OsH), −15.84 (br d, J = 36 Hz, 2H; exchanging Os(μ-H) and
HP
31 1
one OsH group). P{ H} NMR (C D , 161.97 MHz, 20 °C): δ 57.1
6
6
CF
3
CF
3
19
(
(
6
=
m, overlapping
PCP and μ- PCPH resonances). F NMR
3
C D , 376.5 MHz, 20 °C): δ −59.4 (br s, 6F; PCF ), −63.9 (d, J
=
6
6
3
FF
3
3 Hz, 6F; PCF ), −65.3 (d, J = 66 Hz, 6F; PCF ), −65.8 (ps t, J
(7) Gupta, M.; Hagen, C.; Flesher, R. J.; Kaska, W. C.; Jensen, C. M.
Chem. Commun. 1996, 2083.
3
FF
3
FP
38 Hz, 6F; PCF ).
3
G
dx.doi.org/10.1021/om400823s | Organometallics XXXX, XXX, XXX−XXX