A Parahydrogen Study of Catalytic Hydrogenation by Diphosphane-Substituted Triruthenium Clusters
FULL PAPER
[
7]
solvents were used as received. [Ru
phenone (Aldrich) and sodium (Fluka) were also used as received.
The clusters [Ru (CO)10(dppe)] (1) and [Ru (CO) (dppe) ] (2) were
prepared using a literature method and purified by recrystallis-
ation from hexane/dichloromethane. Characterisation was achieved
by comparison of characteristic solution IR (νCO) and FAB MS
with the literature data. NMR measurements were made using
NMR tubes fitted with J. Young Teflon valves and solvents (dried
and degassed) were added by vacuum transfer in a high-vacuum
line. For the PHIP experiments, hydrogen enriched in the para spin
3
(CO)12] (Strem), dppe, benzo-
M. S. Anwar, D. Blazina, H. A. Carteret, S. B. Duckett, T. K.
Halstead, J. A. Jones, C. M. Kozak, R. J. K. Taylor, Phys. Rev.
Lett. 2004, 93, 040501 .
3
3
8
2
[8] [8a]
[
12]
S. Aime, R. Gobetto, D. Canet, J. Am. Chem. Soc. 1998,
1
20, 6770Ϫ6773. [
Russo, A. Viale, D. Canet, J. Phys. Chem. A 1999, 103,
702Ϫ9705.
8b]
S. Aime, W. Dastru, R. Gobetto, A.
9
[9] [9a]
B. Bergman, E. Rosenberg, R. Gobetto, S. Aime, L. Milone,
F. Reineri, Organometallics 2002, 21, 1508Ϫ1511. [ R. Gob-
etto, L. Milone, F. Reineri, L. Salassa, A. Viale, E. Rosenberg,
Organometallics 2002, 21, 1919Ϫ1924.
10] [10a]
9b]
[
C. J. Sleigh, S. B. Duckett, R. J. Mawby, J. P. Lowe, Chem.
2
state was prepared by cooling H to 18 K over activated charcoal.
The studies were carried out with sample concentrations of ap-
proximately 1 µ and spectra were recorded with a Bruker DRX-
Commun. 1999, 1223Ϫ1224. [
10b]
D. Blazina, S. B. Duckett, P.
J. Dyson, B. F. G. Johnson, J. A. B. Lohman, C. J. Sleigh, J.
Am. Chem. Soc. 2001, 123, 9760Ϫ9768. [
10c]
D. Blazina, S. B.
1
13
31
4
00 spectrometer with H at 400.1 MHz, C at 100.1 MHz and
P
Duckett, P. J. Dyson, J. A. B. Lohman, Angew. Chem. Int. Ed.
1
at 162.0 MHz, respectively. H NMR chemical shifts are reported
[10d]
2001, 40, 3874Ϫ3877.
D. Blazina, S. B. Duckett, P. J. Dy-
in ppm relative to residual 1H signals in the deuterated solvents
son, J. A. B. Lohman, Chem. Eur. J. 2003, 9, 1046Ϫ1061.
D. Blazina, S. B. Duckett, P. J. Dyson, J. A. B. Lohman, Dalton
Trans. 2004, 2108Ϫ2114.
12]
13
[11]
([D
7
]toluene: δ ϭ 2.13 ppm; CHCl
3
: δ ϭ 7.27 ppm), C NMR in
ppm relative to CDCl
3
(δ ϭ 77.05 ppm), and 31P NMR in ppm
[
[
downfield of an external 85% solution of phosphoric acid. Modi-
fied COSY, HMQC and EXSY pulse sequences were used as de-
M. I. Bruce, T. W. Hambley, B. K. Nicholson, M. R. Snow, J.
Organomet. Chem. 1982, 235, 83Ϫ91.
13] [13a]
[
24]
H. Adams, S. C. M. Agustinho, B. E. Mann, S. Smith, J.
scribed previously.
EXSY spectra were acquired immediately after exposing the sample
to p-H and introducing it into the NMR probe. The results were
modelled for hydride exchange and hydride transfer into free H
or for hydride transfer into the hydrogenation product, applying
In the exchange and hydrogenation studies,
Organomet. Chem. 2000, 607, 175Ϫ181. [
13b]
H. Adams, S. C.
M. Agustinho, K. Chomka, B. E. Mann, S. Smith, S. E. Spey,
Can. J. Chem. 2001, 79, 760Ϫ774.
B. F. G. Johnson, Y. V. Roberts, J. Chem. Soc., Dalton Trans.
2
2
,
[14]
[15]
1
993, 2945Ϫ2950.
[
10,23]
published procedures.
The rate constants obtained in this way
S. Aime, R. Gobetto, E. Valls, Inorg. Chim. Acta 1998,
were multiplied by two to take into account the analysis method.[
25]
275Ϫ276, 521Ϫ527.
[16] [16a]
M. I. Bruce, E. Horn, O. bin Shawakataly, M. R. Snow, E.
Supporting Information: Lists of raw and simulation data and de-
tails of the analysis method are available for hydride exchange and
H elimination in species 3, 5a and 5b, as well as for catalytic hydro-
2
genation by 6 (footnote on first page of this article).
R. T. Tiekink, M. L. Williams, J. Organomet. Chem. 1986, 316,
187Ϫ211. [
16b]
M. A. Churchill, R. A. Lashewicz, J. R. Shapley,
[
16c]
S. I. Richter, Inorg. Chem. 1980, 19, 1277Ϫ1285.
P. Ho-
manen, R. Persson, M. Haukka, T. A. Pakkanen, E. Nord-
lander, Organometallics 2000, 19, 5568Ϫ5574.
[17]
[17a]
For example, see:
S. Aime, W. Dastru, R. Gobetto, J.
Krause, L. [ Matas, A. Viale, Organometallics 1996, 15,
17b]
Acknowledgments
4967Ϫ4970.
S. Aime, W. Dastru, R. Gobetto, F. Reineri,
A. Russo, A. Viale, Organometallics 2001, 20, 2924Ϫ2927.
N. E. Leadbeater, J. Lewis, P. R. Raithby, J. Organomet. Chem.
1997, 543, 251Ϫ253.
19]
We are grateful to Bruker Biospin and the University of York for
financial support. University scholarships from the ORS award
scheme (D. B.) and Pfizer Central Research (T. G. P.) are gratefully
acknowledged. We also thank Profs. R. N. Perutz, R. Eisenberg, B.
F. G. Johnson for helpful discussions.
[18]
[
[
D. Schott, C. J. Sleigh, J. P. Lowe, S. B. Duckett, R. J. Mawby,
M. G. Partridge, Inorg. Chem. 2002, 41, 2960Ϫ2970.
20] [20a]
N. Lugan, J. J. Bonnet, J. A. Ibers, Organometallics 1988,
20b]
7
, 1538Ϫ1545. [
S. M. Waterman, M. G. Humphrey, J. Lee,
G. E. Ball, D. C. R. Hockless, Organometallics 1999, 18,
[
1]
For example, see: [1a] Catalysis by di- and polynuclear metal clus-
ter complexes (Eds.: R. D. Adams, F. A. Cotton), Wiley-VCH,
New York, 1998. [1b] P. J. Dyson, J. S. McIndoe, Transition me-
tal carbonyl cluster chemistry, Gordon and Breach, Amster-
2440Ϫ2451.
[
21] [21a]
B. T. Heaton, J. A. Iggo, I. S. Podkorytov, D. J. Smawfield,
S. P. Tunik, R. Whyman, J. Chem. Soc., Dalton Trans. 1999,
1917Ϫ1919. [
21b]
D. S. Z. Sabounchei, B. T. Heaton, J. A. Iggo,
dam, 2000.
For example, see:
C. Jacob, I. S. Podkorytov, J. Clust. Sci. 2001, 12, 339Ϫ348.
[
2]
[2a]
[22]
[22a]
M. I. Bruce, P. A. Humphrey, B. W. Skel-
For example, see:
M. I. Bruce, P. A. Humphrey, B. W. Skel-
ton, A. H. White, J. Organomet. Chem. 1996, 522, 259Ϫ263.
ton, A. H. White, M. L. Williams, Aust. J. Chem. 1985, 38,
[2b]
[22b]
M. I. Bruce, P. A. Humphrey, B. W. Skelton, A. H. White,
1301Ϫ1305.
N. Lugan, J. J. Bonnet, J. A. Ibers, J. Am.
J. Organomet. Chem. 1996, 526, 85Ϫ97. [ M. I. Bruce, B. W.
2c]
Chem. Soc. 1985, 107, 4484Ϫ4491.
[22c]
C. Bergounhou, J. J.
Skelton, A. H. White, N. N. Zaitseva, J. Organomet. Chem.
Bonnet, P. Fompeyrine, G. Lavigne, N. Lugan, F. Mansilla, Or-
ganometallics 1986, 5, 60Ϫ66.
1
998, 558, 197Ϫ207.
G. Lavigne, N. Lugan, J. J. Bonnet, Organometallics 1982, 1,
040Ϫ1050.
[
[
3]
[23]
W. D. Jones, G. P. Rosini, J. A. Maguire, Organometallics 1999,
18, 1754Ϫ1760.
1
4] [4a]
[24] [24a]
B. Fontal, M. Reyes, T. Suarez, F. Bellandi, J. C. Diaz, J.
B. A. Messerle, C. J. Sleigh, M. G. Partridge, S. B. Duckett,
Mol. Catal. A: Chem. 1999, 149, 75Ϫ85. [ B. Fontal, M. Re-
yes, T. Suarez, F. Bellandi, N. Ruiz, J. Mol. Catal. A: Chem.
4b]
J. Chem. Soc., Dalton Trans. 1999, 1429Ϫ1435.
[24b]
S. A. Col-
ebrooke, S. B. Duckett, J. A. B. Lohman, Chem. Commun.
2000, 685Ϫ686. [
24c]
P. Hubler, J. Bargon, Angew. Chem. Int.
1
5]
999, 149, 87Ϫ97.
[
[
E. L. Diz, A. Neels, H. Stoeckli-Evans, G. Süss-Fink, Poly-
hedron 2001, 20, 2771Ϫ2780.
Ed. 2000, 39, 3701Ϫ3703.
[25]
M. L. H. Green, L. L. Wong, A. Sella, Organometallics 1992,
11, 2660Ϫ2668.
6] [6a]
J. Natterer, J. Bargon, Prog. Nucl. Magn. Reson. Spectrosc.
6b]
1
997, 31, 293Ϫ315. [ S. B. Duckett, C. J. Sleigh, Prog. Nucl.
Received May 31, 2004
Early View Article
Published Online September 2, 2004
[6c]
Magn. Reson. Spectrosc. 1999, 34, 71Ϫ92.
S. B. Duckett, D.
Blazina, Eur. J. Inorg. Chem. 2003, 2901Ϫ2912.
Eur. J. Inorg. Chem. 2004, 4381Ϫ4387
www.eurjic.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4387