1
166 Organometallics, Vol. 29, No. 5, 2010
Bonnet et al.
1
3
were performed by H. Kolbe Microanalysis Laboratories,
M u€ lheim, Germany. For column chromatography, Merck silica
gel 60 (230-400 mesh) was used. Vinylepoxide, trans-phenyl-
vinylboronic acid, cesium carbonate, and dihexyl ether were
J = 6.8 Hz). C NMR δ(75 MHz; acetone-d
6
): δ 120.2 (i), 113.7
IV
(o), 96.8 (C Cp*), 85.2 (p), 84.1 (m), 45.0 (CH
2
S), 39.72 (CHS),
i
23.2 and 22.9 (CH3 Pr), 10.7 (Me Cp*). F NMR (376 MHz,
19
5
acetone-d ): δ -151.6 (s). MALDI-TOF m/z (calc): 491.25
6
i
71
þ
þ
commercial products. SCS-pincer ligand 2,6-( PrSCH
PCP-pincer palladium precursor [Pd(MeCN)(PCP)](BF
[
2
)C
6
H
4
,1
(491.14, [M - PdCl þ H] ), 631.07 (631.00, [M] ). Anal. C,
9
4
),
H, N: 40.20/5.01/0.0 (exp) 40.12/5.05/0.0 (calc).
[5](PF ): reaction time 7 days; yield 83%. H NMR (400
39
38
1
Ru(C H )(MeCN) ](PF ), and [Ru(C Me )(MeCN) ](PF )
5
5
3
6
5
5
3
6
6
were prepared according to literature procedures.
Complex 1. [Pd(MeCN) ](BF (322 mg, 1 mmol) was dis-
solved in dry, degassed acetonitrile (25 mL) and added under
6
MHz; acetone-d ): δ 6.33 (d, 2H, m, J = 5.8 Hz), 6.15 (t, 1H, p,
4
4
)
2
J = 5.8 Hz), 5.40 (s, 5H, Cp), 3.60 (dt, 2H, CH P, J = 18.6, 3.9
2
0
Hz), 3.47 (dt, 2H, CH P , J = 18.6, 3.9 Hz), 2.57 (m, 2H, CHP),
2
i
0
i
2.44 (m, 2H, CHP ), 1.49 (m, 6H, Pr), 1.39 (m, 6H, Pr ), 1.33 (m,
i
0
nitrogen to the ligand 2,6-( PrSCH ) C H (305 mg, 1.2 equiv).
4
2
2
6
i
6H, Pr ), 1.23 (m, 6H, Pr ). C NMR (100 MHz; acetone-d
00
i
000 13
The orange mixture was heated to 50 °C under nitrogen for 16 h
and turned yellow. Acetonitrile was evaporated under vacuum;
distilled, degassed dichloromethane (50 mL) was added, as well
as degassed brine (25 mL). The biphasic mixture was stirred
vigorously for 1 h, the aqueous layer discarded, and the organic
6
): δ
123.3 (s, ipso), 114.0 (t, ortho, JC-P = 13.1 Hz), 84.2 (t, meta,
J
IV
= 9.2 Hz), 84.1 (s, para), 81.5 (C Cp), 55.0 (CH P, and for
2
C-P
Me (P Pr
i
2
)), 34.8 (s), 32.7 (t, JC-P = 12.2 Hz), 26.7 (t, JC-P = 12.0
Hz), 23.7(t, JC-P = 12.1 Hz), 23.0 (s), 19.2 (t, JC-P = 2.4 Hz), 19.1
19
phase dried over MgSO
4
and evaporated. Reprecipitation from
CH Cl /pentane yielded complex 1 (316 mg, 80%) that was
(t, JC-P = 1.5 Hz), 18.58 (t, JC-P = 1.9 Hz), 18.56, 17.2, 14.27. F
31
NMR (376 MHz, acetone-d ): δ -67.7 (d, J = 708 Hz).
F-P
P
, J =
2
2
6
4
1 1
identical to the published compound.
ppm in acetone-d ): δ 6.99 (m, 3H, arom.), 4.33 (s, 4H, CH2S),
.55 (sept, 2H, CHS( Pr), J = 6.8 Hz), 1.59 (d, 12H, CH ( Pr),
H NMR (400 MHz;
NMR (162 MHz, acetone-d
6
): δ 64.1 (PCP), -138.0 (q, PF
6
þ
6
708 Hz). MALDI-TOF m/z (calc): 610.25 (610.07, [M - Cl] ),
645.20 (645.04, [M] ). Anal. C, H, N: 37.86/5.04/0.0 (exp) 37.99/
5.10/0.0 (calc).
i
i
þ
3
3
13
J = 6.8 Hz). C NMR (100 MHz; ppm in acetone-d ): δ 160.4
6
C
1
(
CHS), 23.0 (CH
i), 150.8 (o), 125.2 (p), 122.7 (m), 43.4 and 43.1 (CH
2
S and
[6](BF
MHz; acetone-d
J = 5.8 Hz), 3.35 (dt, 2H, CH P, J = 18.0, 4.2 Hz), 3.22 (dt, 2H,
4
): reaction time 6 days; yield 85%. H NMR (400
i
( Pr)).
3
6
): δ 5.94 (d, 2H, m, J = 5.8 Hz), 5.80 (t, 1H, p,
Complex 2. [Pd(MeCN)(PCP)](BF ) (171 mg, 300 μmol) was
4
2
0
0
dissolved in distilled, degassed dichloromethane (25 mL), and
brine (20 mL) was cannulated under nitrogen. The biphasic
mixture was stirred vigorously for 1 h, the aqueous phase was
CH
1.98 (s, 15H, Cp*), 1.50 (m, 6H, Pr), 1.39 (m, 12H, Pr and Pr ),
2
P , J = 18.0, 4.2 Hz), 2.57 (m, 2H, CHP), 2.43 (m, 2H, CHP ),
i
i
0
i
00
i
1.16 (m, 6H, Pr ). C NMR (75 MHz; acetone-d
000 13
6
): δ 128.7 (ipso),
IV
= 12.6 Hz), 95.4 (C Cp*), 85.9 (para), 85.3 (t,
removed, and the organic phase was dried over MgSO . Filtra-
4
111.8 (t, ortho, J
C-P
i
tion and removal of the solvent quantitatively afforded 2, which
was identical to the published compound.
2 2
meta, JC-P = 8.7 Hz), 55.0 (CH P), and for Me (P Pr ): 31.5 (t,
4
2 1
H NMR (400
MHz; ppm in acetone-d ): δ 7.00 (d, 2H, m, J = 7.6), 6.88 (t,
JC-P = 11.9 Hz), 27.2 (t, JC-P =11.5Hz),24.2(t,JC-P =12.0Hz),
19.8 (t, J
= 1.6 Hz), 19.5 (t, J
= 2.0 Hz), 19.0 (t, J
= 2.2
6
C-P
C-P
9
C-P
1
1
1
1
H, p, J = 6.9), 3.26 (t, 4H, CH P, J = 4.4), 2.37 (m, 2H, CHP),
2
Hz), 17.6 (s), 10.5 (Me Cp*). F NMR (376 MHz, acetone-d ): δ
5 6
31
-151.4 (s). P NMR (162 MHz, acetone-d
m/z (calc): 679.82 (680.15, [M - Cl] ), 714.85 (715.12, [M] ). Anal.
C, H, N: 44.98/6.25/0.0 (exp) 44.90/6.28/0.0 (calc).
X-ray Crystal Structure Determinations. X-ray reflections
were measured with Mo KR radiation (λ = 0.71073 A) on a
Nonius Kappa CCD diffractometer with rotating anode. The
i
.36 (dd, 12H, J = 16.6, 7.2 Hz), 1.16 (dd, 12H, Me( Pr), J =
6
):δ57.3. MALDI-TOF
3
1
þ
þ
4.6, 7.1 Hz). P NMR (162 MHz; ppm in acetone-d
6
): δ 62.7.
1
3
C NMR (162 MHz; ppm in acetone-d ): δ 160.2 (s, i), 151.6 (t,
6
ortho, J = 10.8 Hz), 125.6 (s, p), 123.2 (t, m, J = 10.8 Hz), 33.8 (t,
CHP, J = 11.6 Hz), 24.7 (t, CH P, J = 11.3 Hz), 19.1 (s, CH
˚
2
3
-
i
i
( Pr)).
(
Pr)), 18.3 (CH
3
þ
þ
General Procedure toward Bimetallic Complexes [3] -[6] . In
a typical experiment, the SCS- or PCP-pincer palladium com-
crystal of [3](PF ) consisted of two crystalline fragments, but
6
only the nonoverlapping intensities of the major fragment were
used. The structures were solved with direct methods (program
SHELXS-97). Refinement was performed with SHELXL-97
plex 1 or 2 (250 μmol) was mixed under nitrogen with
7
2
72
[
Ru(C
H
5 5
)(MeCN)
3
6
](PF )
or [Ru(C
5
Me
5
)(MeCN)
3
](BF
4
)
2
(
275 μmol for 1, 375 μmol for 2) in freshly distilled dichloro-
against F of all reflections. Non-hydrogen atoms were refined
with anisotropic displacement parameters. In [3](PF ), [4](BF ),
methane (5.0 mL) and stirred at room temperature under
nitrogen for 4 to 7 days. The dark solution was directly put on
top of a 50 mL silica gel column and eluted with dichloro-
methane containing 1-2% methanol. Traces of starting pincer
material eluted first, followed by the bimetallic complex. The
product was reprecipitated from dichloromethane/pentane to
6
4
and [5](PF
Fourier maps. In [6](BF
in calculated positions. In [3](PF ) and [5](PF ) the hydrogen
6
) all hydrogen atoms were located in difference
4
) the hydrogen atoms were introduced
6
6
atoms of the Ru-coordinated phenyl and cyclopentadienyl rings
were refined freely with isotropic displacement parameters, and
all other H atoms were refined as rigid groups. In [4](BF ) and
4
þ
þ
yield [3] -[6] as whitish, air-stable powders.
1
): reaction time 7 days; yield 82%. H NMR (400
[
MHz; ppm in acetone-d
3](PF
6
[
[
6](BF ) all hydrogen atoms were refined as rigid groups. In
4
6
): δ 6.34 (d, 2H, m, J = 5.9), 6.16 (t, 1H,
4](BF
4 6
) and [5](PF ) the anions were refined with a disorder
p, J = 5.9Hz), 5.54 (s, 5H, Cp), 4.55 (d, 2H, CH
0
2
S, J = 16.2 Hz),
model using strong distance and angle restraints. Geometry
calculations and checking for higher symmetry were performed
with the PLATON program. Further details are given in
4.42 (d, 2H, CH S , J = 16.6 Hz), 3.70 (sept, 2H, CHS, J = 6.8
0
Hz), 1.67 (d, 6H, Me, J = 6.8 Hz), 1.63 (d, 6H, Me , J = 6.8 Hz).
2
73
1
3
C NMR (75 MHz; ppm in acetone-d
6
): δ 118.4 (i), 113.7 (o),
Table 1 and Table S1 (Supporting Information).
Catalytic Experiments. Eight experiments were run simulta-
neously using a ChemSpeed automated sampler. In each reaction
IV
8
3.5 (p), 83.0 (m), 82.1 (C i Cp), 55.0 (CH S), 44.5 and 41.3
2
31
(
CHS), 23.2 and 22.8 (CH Pr). P NMR (162 MHz, ppm in
3
acetone-d
calc): 421.20 (421.06, [M - PdCl þ H] ), 561.06 (560.92, [M] ).
Anal. C, H, N: 32.21/3.63/0.0 (exp) 32.30/3.71/0.0 (calc).
6
): δ -143.16 (q, JF-P = 708 Hz). MALDI-TOF m/z
vessel, Cs
(
(
2
CO
1.5 mLof a 1.06 M solutionintetrahydrofuran, 1.6mmol), water
400 μL), dihexyl ether (100 μL, internal reference), and vinyl-
3
(1.04 g, 3.2 mmol), trans-phenylvinylboronic acid
þ
þ
(
1
[
4](BF
MHz; acetone-d
4
): reaction time 4 days; yield 88%. H NMR (400
): δ 5.97 (d, 2H, m, J = 5.9 Hz), 5.82 (t, 1H, p,
expoxide (160 μL, 1.2 equiv) were added one after another.
Subsequently, 1 or 0.25 mol % of palladium catalyst was added
as a solid, and the vial containing the catalyst was rinsed with
1.5 mL of tetrahydrofuran that was added to the vessel. After
preparation of the eight vessels, the vessel holder was mounted on
6
J = 5.9 Hz), 4.48 (d, 2H, CH
0
2
S, J = 16.7 Hz), 4.20 (d, 2H,
CH S , J = 16.7 Hz), 3.71 (sept, 2H, CHS, J = 6.8 Hz), 2.06 (s,
2
0
1
5H, Cp*), 1.69 (d, 6H, Me, J = 6.8 Hz), 1.63 (d, 6H, Me ,
(
71) Evans, D. R.; Huang, M.; Seganish, W. M.; Chege, E. W.; Lam,
(72) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112.
(73) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7.
Y.-F.; Fettinger, J. C.; Williams, T. L. Inorg. Chem. 2002, 41, 2633.