832 Organometallics, Vol. 30, No. 4, 2011
Table 4. Crystal, Measurement, and Refinement Data for the Compounds Studied by X-ray Diffraction
Cabeza et al.
1
3
4[BF4]3
formula
fw
cryst syst
space group
a, A
b, A
C28H19N2O10PRu3
877.63
monoclinic
P21/n
11.5695(1),
15.2004(1)
17.9373(1)
90, 105.220(1), 90
3043.83(4)
4
C26H19N2O8PRu3
821.61
orthorhombic
Pbca
14.0159(1)
17.3425(2)
23.5717(2)
90, 90, 90
5729.59(9)
8
C63H60B3F12N6O9P3Ru3
1701.72
trigonal
P-3C1
14.825(1)
14.825(1)
41.080(3)
90, 90, 120
7819.0(9)
4
c, A
R, β, γ, deg
V, A3
Z
F(000)
1712
1.915
3200
1.905
3408
1.446
Dcalcd, g cm-3
μ (Cu KR), mm-1
cryst size, mm
T, K
12.917
0.27 ꢀ 0.20 ꢀ 0.08
13.615
0.10 ꢀ 0.08 ꢀ 0.05
5.920
0.09 ꢀ 0.07 ꢀ 0.03
293(2)
293(2)
293(2)
θ range, deg
min./max. h, k, l
no. collected reflns
no. unique reflns
no. reflns with I > 2σ(I)
no. params/restraints
GOF on F2
R1 (on F, I > 2σ(I))
wR2 (on F2, all data)
max./min. ΔF, e A-3
3.87 to 73.95
-12/14, -18/18, -21/20
11 147
5914
5406
398/0
1.045
0.0374
0.1084
3.15 to 73.88
-17/17, -21/21, -29/27
61 252
5796
5699
369/0
1.096
0.0242
0.0634
3.23 to 73.82
-14/0, 0/16, 0/46
3860
3860
2702
316/83
1.044
0.0962
0.2964
-0.984/1.010
-0.715/0.640
-1.030/1.350
[Ru3(CO)12] (376 mg, 0.588 mmol) was added. The mixture was
stirred for 2 h. The color changed from orange to yellow. The
solid of the resulting suspension was filtered off, and the filtrate
was evaporated to dryness to give a yellow solid, which was
washed with hexane (3 ꢀ 20 mL) and vacuum-dried (695 mg,
82%). Anal. Calcd for C21H19N2O3PRu (479.44): C, 52.61; H,
3.99; N, 5.84. Found: C, 52.68; H, 4.03; N, 5.79. IR (THF): νCO
1998 (s), 1909 (s), 1883 (vs). 1H NMR (CD2Cl2, 293 K): δ 7.68
(m, 4 H), 7.52-7.40 (m, 6 H), 7.02 (d, J = 1.6 Hz, 1 H), 6.93 (d,
J = 1.6 Hz, 1 H), 4.07 (m, 1 H), 4.00 (m, 1 H), 3.97 (s, 3 H), 2.52
(m, 2 H). 31P{1H} NMR (CD2Cl2, 293 K): δ 30.0 (s). 13C{1H}
and DEPT NMR (CD2Cl2, 193 K): δ 214.2 (d, J = 9 Hz, CO),
176.3 (d, J = 16 Hz, C), 139.4 (d, J = 32 Hz, C), 132.4 (d, J = 14
Hz, CH), 129.3 (s, CH), 128.3 (d, J = 10 Hz, CH), 122.6 (s, CH),
121.7 (s, CH), 47.9 (d, J = 10 Hz, CH2), 39.6 (s, CH3), 28.8 (d,
J = 20 Hz, CH2).
vacuum-dried (77 mg, 40%). Anal. Calcd for C63H60B3F12-
N6O9P3Ru3 (1701.75): C, 44.47; H, 3.55; N, 4.94. Found: C,
44.53; H, 3.63; N, 4.88. IR (CH2Cl2): νCO 2045 (w), 2023 (w),
1
1981 (vs), 1968 (vs). H NMR (CD2Cl2, 293 K): δ 8.67 (s, br,
1 H), 7.56-7.45 (m, 10 H), 7.17 (m, 1 H), 7.06 (m, 1 H), 4.09 (m,
2 H), 3.91 (s, 3 H), 3.14 (m, 2 H). 31P{1H} NMR (CD2Cl2, 293
K): δ 21.9 (s). 13C{1H} and DEPT NMR (CD2Cl2, 293 K): δ
136.9 (s, CH), 134.8 (d, J = 43 Hz, C), 132.4 (d, J = 11 Hz, CH),
131.0 (CH), 129.3 (d, J = 10 Hz, CH), 123.9 (CH), 122.4 (CH),
46.1 (d, J = 5 Hz, CH2), 36.7 (CH3), 34.0 (d, J = 20 Hz, CH2).
Deprotonation of 4[BF4]3. A suspension of 4[BF4]3 (616 mg,
0.362 mmol) in THF (30 mL) was treated with a toluene solution
of K[N(SiMe3)2] (2.3 mL, 0.5 M, 1.150 mmol). Immediately, the
solid dissolved to give a yellow solution. An IR analysis of this
solution indicated the complete transformation of 4[BF4]3 into
compound 2.
Synthesis of [Ru3(μ-H)2(μ3-K3C2,P-dppeImCH)(CO)8] (3). A
THF solution (30 mL) of compound 1 (24 mg, 0.029) was stirred
at reflux temperature for 20 min. No color change was observed.
The solvent was removed under reduced pressure, and the solid
residue was washed with hexane (2 ꢀ 15 mL) to give compound 3
as an orange solid (19 mg, 85%). Anal. Calcd for C26H19N2O8-
PRu3 (821.63): C, 38.01; H, 2.33; N, 3.41. Found: C, 38.32; H,
2.47; N, 3.09. (þ)-FAB-MS: m/z 822 [M - H]þ. IR (THF): νCO
2079 (m), 2065 (w), 2038 (vs), 2009 (s), 2000 (s), 1972 (m), 1954
(w). 1H NMR (CD2Cl2, 293 K): δ 7.74-7.64 (m, 3 H), 7.58-7.50
(m, 3 H), 7.48-7.39 (m, 4 H), 7.05 (s, br, 1 H), 6.92 (d, J = 1.6
Hz, 1 H), 6.51 (s, 1 H), 4.22 (ddt, J = 32.1, 14.3, 3.6 Hz, 1 H),
3.98 (m, 1 H), 3.06 (m, 1 H), 1.96 (m, 1 H), -12,19 (s, br, 1 H,
μ-H), -16.76 (s, br, 1 H, μ-H). 31P{1H} NMR (CD2Cl2, 293 K):
δ 28.6 (s). 13C{1H} and DEPT NMR (CD2Cl2, 293 K): δ 206.5
(d, J = 4 Hz, CO); 205.3 (d, J = 7 Hz, CO); 202.4 (s, CO), 202.1
(s, CO); 193.7 (s, CO); 193.6 (s, CO); 188.4 (d, J = 8 Hz, CO);
186.0 (s, CO), 173.9 (d, J = 13 Hz, C); 131.6 (d, J = 12 Hz, CH);
130.0 (d, J = 24 Hz, C); 128.8 (d, J = 9 Hz, CH), 128.5 (d, J =
10 Hz, CH), 118.6 (s, CH), 118.10 (s, CH), 107.2 (s, CH), 47.0 (s,
CH2), 29.4 (d, J = 27 Hz, CH2).
Computational Details. The optimized structures were calcu-
lated by hybrid DFT, within the GAUSSIAN-03 program
suite,34 using Becke’s three-parameter hybrid exchange-
correlation functional35 and the B3LYP nonlocal gradient
correction.36 The LanL2DZ basis set, with relativistic effective
core potentials, was used for the Ru atoms.37 The basis set used
for the remaining atoms was the standard 6-31G with addition of
(d,p)-polarization. To determine the structure of compound 2,
(34) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.;
Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.;
Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson,
G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.;
Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai,
H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, E. R.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.;
Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.;
Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas,
O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.;
Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov,
B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.;
Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.;
Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M.;
Gonzalez, W. C.; Pople, J. A. GAUSSIAN-03 (Revision C2); Gaussian
Inc.: Wallingford, CT, USA, 2004.
Synthesis of [Ru3(KP-dppeHImMe)3(CO)9][BF4]3 (4[BF4]3). A
mixture of [dppeHImMe][BF4] (130 mg, 0.340 mmol) and finely
powdered [Ru3(CO)12] (72 mg, 0.113 mmol) was stirred in THF
(30 mL) at reflux temperature for 1 h. The color changed
from orange to dark violet. After cooling to room temperature,
the solid was filtered, washed with hexane (2 ꢀ 20 mL), and
(35) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
(36) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev., B 1988, 37, 785.
(37) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.