Dalton Transactions
Paper
phenone was removed and the dark red crude product was
then purified by column chromatography on silica gel eluting
(d) B. Rybtchinski and D. Milstein, Angew. Chem., Int. Ed.,
1999, 38, 870–883.
with hexane/CH
Rh(tmp)(COPh) 6b (1.2 mg, 0.0012 mmol, 13% yield).
2
Cl
2
(1 : 1) to give the reddish purple solid of
2 L. E. J. Brouwer, The Petroleum Handbook, Shell Co. of Hong
Kong, London, 5th edn, 1966.
3
B. S. Appel, T. N. Adams, M. J. Roberts, W. F. Lange,
J. H. Freiss, C. T. Einfeldt and M. C. Carnesi, Process for
Conversion of Organic, Waste, or Low-value Materials into
Useful Products, U.S. Patent 8003833, 2011.
Preparation of Rh(tmp)(COMe) (6c) from 2,4-pentanedione
II
Into the benzene solution of Rh (tmp) 3 (0.0045 mmol), PPh
3
(
1.2 mg, 0.0050 mmol) was added and the reaction mixture
4
5
Y. R. Luo, Comprehensive Handbook of Chemical Bond Ener-
gies, CRC Press, Boca Raton, FL, 2007.
(a) B. Rybtchinski, A. Vigalok, Y. Ben-David and
D. Milstein, J. Am. Chem. Soc., 1996, 118, 12406–12415;
was stirred at 25 °C. After 10 min, the benzene solvent was
removed by vacuum evaporation and then degassed 2,4-penta-
nedione (1.0 mL) and H O (4 μL) were added. The mixture was
then stirred under nitrogen at 25 °C for 10 min. Excess 2,4-
pentanedione was removed and there was no Rh(tmp)(COMe)
in the dark red crude product.
2
(
b) B. Rybtchinski and D. Milstein, Angew. Chem., Int. Ed.,
999, 38, 870–883.
(a) L. Cassar, P. E. Eaton and J. Halpern, J. Am. Chem. Soc.,
970, 92, 3515–3518; (b) H. Ogoshi, J. Setsume and
Z. Yoshida, J. Chem. Soc., Chem. Commun., 1975, 572–573;
c) C. Perthuisot and D. A. Sweigart, Organometallics, 1999,
8, 4887–4888.
1
6
1
Preparation of Rh(tmp)(COMe) (6c) from 3-methyl-2,4-
pentanedione
(
1
II
Into the benzene solution of Rh (tmp) 3 (0.0045 mmol), PPh
3
(1.2 mg, 0.0050 mmol) was added and the reaction mixture
7
8
P. Eilbracht and P. Dahler, Chem. Ber., 1980, 113, 542–554.
F. W. S. Benfield and M. L. H. Green, J. Chem. Soc., Dalton
Trans., 1974, 1324–1331.
was stirred at 25 °C. After 10 min, the benzene solvent was
removed by vacuum evaporation and then degassed 3-methyl-
2
mixture was then stirred under nitrogen at 25 °C for 10 min.
Excess 3-methyl-2,4-pentanedione was removed and there was
no Rh(tmp)(COMe) in the dark red crude product.
2
,4-pentanedione (1.0 mL) and H O (4 μL) were added. The
9
(a) J. W. Suggs and C. H. Jun, J. Am. Chem. Soc., 1984, 106,
3
1
054–3056; (b) J. W. Suggs and C. H. Jun, J. Am. Chem. Soc.,
986, 108, 4679–4681; (c) J. W. Suggs, M. J. Wovkulich and
S. D. Cox, Organometallics, 1985, 4, 1101–1107.
0 (a) M. Murakami, H. Amii and Y. Ito, Nature, 1994, 370,
41–542; (b) M. Murakami, T. Tsuruta and Y. Ito, Angew.
Chem., Int. Ed., 2000, 39, 2484–2486.
1
Preparation of (PPh )Rh(tmp)OH (7)
3
5
II
Into
a
benzene-d6 solution (500 μL) of Rh (tmp)
(0.00056 mmol) at r.t., the degassed benzene-d
6
solution 11 A. Sachio and U. Kazuaki, Preparation of Lower Fatty Acids
(
500 μL) of H O (4 μL) and PPh (0.1 mg, 0.00044 mmol) was
2
3
From Lower Aliphatic Ketones, Jpn. Kokai Tokkyo Koho 06-
added. The mixture was kept under nitrogen at 25 °C. Immedi-
329577, 1994.
1
ately, the color changed from dark orange to red. H NMR of 12 H. S. Fung, B. Z. Li and K. S. Chan, Organometallics, 2010,
PPh )Rh(tmp)OH (C , 400 MHz) δ 1.92 (s, 12 H), 2.14 (s, 12 29, 4421–4423.
H), 2.43 (s, 12 H), 8.83 (s, 8 H). The (PPh )Rh(tmp)O–H signal 13 C. S. Chan, S. Y. Lee and K. S. Chan, Organometallics, 2013,
(
3
6 6
D
3
1
is not observed in the H NMR spectrum, likely due to the
32, 151–156.
rapid exchange with water. HRMS (ESI-MS) result: calcd for 14 S. Y. Lee, T. H. Lai, K. S. Choi and K. S. Chan, Organometal-
+
C H N OPRh [M] m/z 1162.4180. Found m/z 1162.4194.
lics, 2011, 30, 3691–3693.
7
4
68 4
15 S. Y. Lee and K. S. Chan, Organometallics, 2013, 32, 5391–
5
401.
6 (a) H. S. Fung, B. Z. Li and K. S. Chan, Organometallics,
010, 29, 4421–4423; (b) H. S. Fung, B. Z. Li and K. S. Chan,
Organometallics, 2012, 31, 570–579.
17 L. Zhang and K. S. Chan, J. Organomet. Chem., 2006, 691,
785–3787.
1
Acknowledgements
2
We thank the Research Grants Council of the HKSAR (CUHK
4
00113) for financial support.
3
18 K. S. Choi, T. H. Lai, S. Y. Lee and K. S. Chan, Organometal-
lics, 2011, 30, 2633–2635.
Notes and references
1
9 (a) R. W. Wagner, D. S. Lawrence and J. S. Lindsey, Tetrahe-
dron Lett., 1987, 28, 3069–3070; (b) K. S. Chan, X. M. Chen
and T. C. W. Mak, Polyhedron, 1992, 11, 2703–2716.
1
(a) J. H. Sinfelt, in Catalysis-Science and Technology, ed.
J. R. Anderson and M. Boudart, Springer-Verlag, West
Berlin, 1981, vol. 1, ch. 5, pp. 257–300; (b) M. Murakam 20 (a) X. Zhou, Q. Li, T. C. W. Mak and K. S. Chan, Inorg.
and Y. Ito, in Topics in Organometallic Chemistry, Vol. 3,
Cleavage of Carbon–Carbon Single Bonds by Transition
Metals, ed. S. Murai, Springer-Verlag, Berlin Heidelberg,
Chim. Acta, 1998, 270, 551–554; (b) X. Zhou, R.-J. Wang,
F. Xue, T. C. W. Mak and K. S. Chan, J. Organomet. Chem.,
1999, 580, 22–25.
1
999, pp. 97–129; (c) M. Gozin, A. Weisman, Y. Ben-David 21 B. B. Wayland, A. E. Sherry, G. Poszmik and A. G. Bunn,
and D. Milstein, Nature, 1993, 364, 699–701;
J. Am. Chem. Soc., 1992, 114, 1673–1681.
This journal is © The Royal Society of Chemistry 2016
Dalton Trans., 2016, 45, 3522–3527 | 3527