272
P. Frediani et al. / Journal of Organometallic Chemistry 584 (1999) 265–273
IR (benzene solution) in the 2200–1500 cm−1 region:
1992(s), 1922(vs) cm−1 31P-NMR (CD2Cl2 solution) a
The IR spectrum (C6H12 as solvent) showed the
following carbonyl stretching frequencies: 2057(s),
2020(s), 2009(vs), 1998(s), 1968(s), 1955(s) cm−1
;
1
singlet at l 22.0 ppm; H-NMR (CD2Cl2 solution) l
7.90–7.60 (m, 2 H, Harom), 7.40–7.10 (m, 4 H, Harom),
1.65 (s, 12 H, PCH2), 1.35 (s, 24 H, CH2CH2CH3), 0.90
(s, 18 H, CH3), ppm; In the 13C-NMR (CD2Cl2 solu-
tion) l 199.5 (t, CO, JCP=11.4 Hz), 140.1 (s, Carom),
140.0 (s, Carom), 128.7 (s, CHarom), 126.7 (s, CHarom),
124.5 (s, CHarom), 124.2 (s, CHarom), 124.0 (s, CHarom),
122.8 (s, CHarom) ppm. The resonances of the PBu3
ligand are present in the usual range between l 30 and
14 ppm. These data are in agreement with the formula-
tion Ru(CO)2(BT)(PBu3)2 (9).
.
The 31P-NMR spectrum (C6D6 as solvent) displayed
l 33.6 (s, 1P) and 15.4 (s, 1P) ppm; The 1H-NMR
spectrum (CDCl3 as solvent) displayed l 7.82 (m, 4H),
7.51 (m, 4H), 7.00 (t, 14H, JHH=5.8 Hz) and 6.25 (dd,
2H, JHH=5.8 Hz, JHH=3.4 Hz) ppm. The IR and
1H-NMR data are in agreement with those reported by
Bruce [10] for Ru3(CO)7 (m3-C6H4)(m-PPh2)2.
Acknowledgements
MS m/z (%): 696 (1) [M]+, 668 (2) [M–CO]+, 640
(2) [M–2CO]+, 562 (50) [M–BT]+, 534 (100)
[Ru(CO)(PBu3)2]+, 505 (20) [Ru(PBu3)2]+, (centers of
each ruthenium cluster peaks are reported).
This work was partially supported by MURST.
References
4.4.3. Reaction of Ru(CO)2(BT)(PPh3)2 (8) with H2
A benzene solution (5 ml) of 8 (50 mg) was heated at
50°C in the presence of hydrogen (5 atm) for 18 h. The
solution was analyzed by 31P-NMR. A partial transfor-
mation (70%) of the starting complex into the dihydri-
doruthenium complex H2Ru(CO)2(PPh3)2 (3) was
detected.
[1] (a) A.N. Startsev, Catal. Rev. Sci. Eng. 37 (1995) 353. (b) C.
Giavarini, A. Girelli, in: La Raffinazione del Petrolio, ESA,
Milan, 1991, p. 147. (c) C. Chattopadhyay, Hydr. Proc. 2 (1987)
49. (d) E. Furimsky, Catal. Rev. Sci. Eng. 25 (1983) 421. (e) E.
Furimsky, C.H. Amberg, Can. J. Chem. 54 (1976) 1507.
[2] (a) C. Bianchini, J.A. Casares, A. Meli, V. Sernau, F. Vizza,
R.A. Sanchez-Delgado, Polyhedron 16 (1997) 3099. (b) C. Bian-
chini, A. Meli, J. Chem. Soc. Dalton Trans. (1996) 801. (c) R.A.
Sanchez-Delgado, J. Mol. Catal. 86 (1994) 287. (d) C. Bianchini,
A. Meli, M. Peruzzini, F. Vizza, S. Moneti, V. Herrera, R.A.
Sanchez-Delgado, J. Am. Chem. Soc. 116 (1994) 4370.
[3] (a) R.A. Sanchez-Delgado, E. Gonza`lez, Polyhedron 8 (1989)
1431. (b) R.H. Fish, J.L. Tan, A.D. Thormodsen, Organometal-
lics, 4 (1985) 1743.
[4] (a) T.A. Pecoraro, R.R. Chianelli, J. Catal. 67 (1981) 430. (b) S.
Harris, R.R. Chianelli, J. Catal. 86 (1984) 400.
[5] C. Bianchini, XXXIII ICCC, Florence 08.30.1998/09.04.1998,
Abstracts, p.11.
[6] (a) A. Salvini, P. Frediani, M. Bianchi, F. Piacenti, Inorg. Chim.
Acta 227 (1994) 247. (b) M. Bianchi, G. Menchi, F. Francalanci,
F. Piacenti, U. Matteoli, P. Frediani, C. Botteghi, J.
Organometal. Chem. 188 (1980) 109. (c) P. Frediani, U. Matte-
oli, M. Bianchi, F. Piacenti, G. Menchi, J. Organometal. Chem.
150 (1978) 273. (d) R.A. Sanchez-Delgado, J.S. Bradley, G.
Wilkinson, J. Chem. Soc. Dalton Trans. (1976) 399.
4.4.4. Identification of the ruthenium complexes in the
reaction crude of a HDS experiment
Following the procedure above reported 34.5 mg
(0.0585 mmol) of Ru(CO)3(PBu3)2 (2), 0.7848 mg (5.85
mmol) of BT and 10 ml of benzene were introduced in
the autoclave. The vessel was pressurized with hydro-
gen (100 bar) and heated at 150°C for 5 h. A sample of
the solution was evaporated to dryness and the residue
1
dissolved in C6D6 and analyzed by H- and 31P-NMR.
In the 31P-NMR spectrum singlets at l 33.9, 33.3, 25.5,
and 23.8 ppm were found. The signal at l 33.9 ppm
may be attributed to the starting complex (2), that at l
33.3 ppm to H2Ru(CO)2(PBu3)2 (4), and that one at l
23.8 ppm to Ru(CO)2(O2)(PBu3)2 formed in the work-
1
ing up of the solution. In the H-NMR spectra a triplet
[7] F. Porta, S. Cenini, S. Giordano, M. Pizzotti, J. Organometal.
Chem. 150 (1978) 261.
[8] P. Frediani, C. Faggi, A. Salvini, M. Bianchi, F. Piacenti, Inorg.
Chim. Acta 272 (1998) 141.
[9] F. Piacenti, M. Bianchi, E. Benedetti, G. Braca, Inorg. Chem. 7
(1968) 1815.
[10] M.I. Bruce, J.M. Guss, R. Mason, B.W. Skelton, A.H. White, J.
Organomet. Chem. 251 (1983) 261.
at l −7.9 ppm (JHP=25 Hz) may be attributed to the
hydride complex 4. The signal at l 25.5 ppm may be
attributed to a ruthenium complex containing BT, un-
1
fortunately in the H-NMR is not possible to identify
the corresponding signals.
[11] (a) C. Bianchini, A. Meli, in: B. Cornils, W.A. Herrmann (Eds.),
Applied Homogeneous Catalysis with Organometallic Com-
pounds, vol. 2, VCH, Weinheim, 1996, p. 969. (b) R.J. Angelici,
Bull. Chem. Soc. Belg. 104 (1995) 265. (c) R.J. Angelici, in: R.B.
King (Ed.), Encyclopedia of Inorganic Chemistry, vol. 3, Wiley,
New York, 1994, p. 1433; (d) T.B. Rauchfuss, Prog. Inorg.
Chem. 39 (1991) 259. (e) R.J. Angelici, Coord. Chem. Rev. 105
(1990) 61. (f) R.J. Angelici, Acc. Chem. Res. 21 (1988) 387.
[12] V. Herrera, A. Fuentes, M. Rosales, R.A. Sanchez-Delgado, C.
Bianchini, A. Meli, F. Vizza, Organometallics 16 (1997) 2465.
4.4.5. Reaction of Ru3(CO)9(PPh3)3 (5) with BT
A benzene solution (20 ml) containing (5) (200 mg)
and BT (100 mg) was heated at reflux temperature for
24 h. The solution was evaporated to dryness and the
products separated by tlc using SiO2 as stationary
phase and hexane/benzene (2:1) as solvent. An orange
product was separated and crystallized from CH2Cl2–
pentane.