−3
−1
˚
The same procedure was followed for the comparative experi-
ments with the dppm/Pd(OAc)2 system.
Dc = 1.710 g cm , l = 4.880 mm , Z = 8, k = 0.71073 A, T =
198(2) K, 22018 reflections collected ( h, k, l), [(sinh)/k] =
−1
˚
0.66 A , 7798 independent (Rint = 0.051) and 6003 observed
reflections [I ≥ 2r(I)], 333 refined parameters, R = 0.046, wR2 =
Acknowledgements
0.133.
Financial support from the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie is gratefully acknowl-
edged.
Preparation of [bis(diphenylphosphino)acetonitrile]-g5-
(pentamethylcyclopentadienyl)ruthenium(II) chloride (8)
(1,5-cod)RuCp*(Cl) (7) (0.23 g, 0.61 mmol) was dissolved in
a Schlenk flask in 40 mL of THF. Bis(diphenylphosphino)–
acetonitrile (1) (0.25 g, 0.61 mmol) was added under argon and the
reaction mixture stirred for 1.5 h at ambient temperature. Solvent
was removed in vacuo and the remaining orange–red solid was
washed with pentane (3 × 20 mL) and dried in vacuo to give the
product 8 as an orange-colored air sensitive solid (0.27 g, 66%).
Mp: 279 ◦C (DSC); (Found: C, 62.44; H, 5.37; N, 2.07. Calc. for
C36H36ClNP2Ru: C, 63.48; H, 5.33; N: 2.06%); dH (599.9 MHz,
d8-toluene/d8-THF, 298 K) 7.63 (m, 4H, o-Ph1), 7.42 (m, 2H, p-
Ph2), 7.40 (m, 4H, o-Ph2), 7.37 (m, 6H, m-Ph1 and p-Ph1), 7.32 (m,
4H, m-Ph2), 5.59 (t, 2JP,H = 10.7 Hz, H-1), 1.75 (t, 4JP,H = 1.9 Hz,
15H, CH3); dC (150.8 MHz, d8-toluene/d8-THF, 298 K) 134.8 (d,
1JP,C = 22.5 Hz, i-Ph1), 134.7 (m, o-Ph2), 133.7 (d, 1JP,C = 17.1 Hz,
i-Ph2), 133.5 (m, o-Ph1), 131.1 (s, p-Ph2), 130.5 (s, p-Ph1), 128.50
(m, m-Ph1), 128.45 (m, m-Ph2), 116.4 (t, 2JP,C = 9.8 Hz, C2), 90.3
(t, 2JP,C = 2.7 Hz, CMe), 49.9 (t, 1JP,C = 7.3 Hz, C1), 10.7 (s, CH3);
dP{1H} (81.0 MHz, d8-toluene, d8-THF, 298 K) 31.3; IR (KBr), m˜
(cm−1): 3051, 2956, 2904, 2223, 1586, 1479, 1434, 1093, 1023, 743,
693, 535, 506.
References
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X-Ray crystal structure analysis of 8 (single crystals were
obtained by slow evaporation of the solvent from a saturated
solution of 8 in THF): Crystal data for C36H36NP2ClRu·0.5C4H8O,
¯
M = 717.17, triclinic, space group P1 (No. 2), a = 10.500(1), b =
˚
˚
16.922(1), c = 20.542(1) A, a = 95.98(1), b = 103.71(1), c =
◦
3
−3
−1
104.75(1) , V = 3376.1(4) A , Dc = 1.411 g cm , l = 0.668 mm ,
˚
Z = 4, k = 0.71073 A, T = 198(2) K, 36224 reflections collected
−1
˚
( h, k, l), [(sinh)/k] = 0.67 A , 16058 independent (Rint
=
0.051) and 11274 observed reflections [I ≥ 2r(I)], 794 refined
parameters, R = 0.047, wR2 = 0.109.
CCDC reference numbers 631765–631768.
For crystallographic data in CIF or other electronic format see
DOI: 10.1039/b616847g
10 J. Ruiz, V. Riera, M. Vivanco, S. Garcia-Granda and M. A. Salvado´,
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4562. See also: Y.-F Yu, A. Wojcicki, M. Calligaris and G. Nardin,
Organometallics, 1986, 5, 47.
Suzuki–Miyaura coupling
A Schlenk flask fitted with a reflux condenser was charged
with 1.00 g (6.36 mmol) of bromobenzene, 0.96 g (7.87 mmol,
1.2 equiv.) of phenylboronic acid, 1.82 g (13.2 mmol, 2 equiv.) of
potassium carbonate and the catalyst solution, in situ generated
from Pd(OAc)2 and dppmCN (1) (1 : 1 molar ratio) in a small
volume of dichloromethane and dry toluene (60 mL). The reaction
mixture was kept at 110 ◦C for 4 h (with regularly taken samples).
The reaction mixture was worked up by adding 50 mL of H2O. The
phases were separated and the aqueous phase extracted with
dichloromethane (3 × 50 mL). The combined organic phases
were dried over MgSO4, filtered and the solvent removed in vacuo.
The biphenyl product was purified by chromatography (silica gel,
dichloromethane/pentane 2 : 1).
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1414 | Dalton Trans., 2007, 1409–1415
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