RSC Advances
Paper
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1 Y. Zhu, X. Kong, X. Li, G. Ding, Y. Zhu and Y. Li, ACS Catal.,
2
4
. Conclusions
014, 4, 3612–3620.
In summary, the reactivity of diphosphine modied Rh-based 12 Z. Wang, G. Li, X. Liu, Y. Huang, A. Wang, W. Chu, X. Wang
catalyst was studied, and the corresponding single crystals of
and N. Li, Catal. Commun., 2014, 43, 38–41.
Rh complexes were prepared. By combining catalytic measure- 13 K. Zhang, H. Zhang, H. Ma, W. Ying and D. Fang, Catal. Lett.,
ments with multiple characterization techniques on the ob-
2014, 144, 691–701.
tained complexes, we have established a structure–catalytic 14 I. Wender, R. Friedel and M. Orchin, Science, 1951, 113, 206.
performance relationship and elucidated the nature of ligand 15 J. Berty and L. Marko, Chem. Technol., 1956, 8, 260.
effects in the ligand modied Rh-based catalysts for reductive 16 M. R ¨o per, H. Loevenich and J. Korff, J. Mol. Catal., 1982, 17,
carbonylation of methanol to ethanol. The diphosphine ligand
with the appropriate number of methylene between two phos- 17 Y. Sugi, K.-i. Bando and Y. Takami, Chem. Lett., 1981, 10, 63–
phorus atoms can enhance the catalyst stability and thus
64.
315–322.
improve the TOF. The edge-exposed phenyl groups of diphos- 18 G. Doyle, J. Mol. Catal., 1983, 18, 251–258.
phine ligand create the steric congestions in the position trans 19 M. Halttunen, M. Niemel ¨a , A. Krause and A. Vuori, J. Mol.
to the acetyl group, which favors the reaction of rhodium with
H and thus promotes the ethanol/acetaldehyde formation. The 20 J. Pursiainen, K. Karjalainen and T. A. Pakkanen, J.
Catal. A: Chem., 1996, 109, 209–217.
2
insights revealed here could open a new avenue for rational
Organomet. Chem., 1986, 314, 227–230.
selection of ligand to obtain the Rh-based catalysts with the 21 K. G. Moloy and R. W. Wegman, Organometallics, 1989, 8,
enhanced formation of ethanol.
2883–2892.
2
2
2
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2 K. G. Moloy and R. W. Wegman, Adv. Chem. Ser., 1992, 230,
323–336.
Conflicts of interest
3 K. G. Moloy and J. L. Petersen, Organometallics, 1995, 14,
2931–2936.
4 F. Porta, S. Tollari, C. Bianchi and S. Recchia, Inorg. Chim.
Acta, 1996, 249, 79–83.
There are no conicts to declare.
Acknowledgements
5 P. G. Gassman, D. W. Macomber and S. M. Willging, J. Am.
This work was supported by the Shanghai Pujiang Program
Chem. Soc., 1985, 107, 2380–2388.
(14PJD011) and the Fundamental Research Funds for the 26 G. Gallaher, J. G. Goodwin, C.-S. Huang and M. Houalla, J.
Central Universities (222201717013). We wishes to thank Dr
Catal., 1991, 127, 719–731.
Xuezhi Duan for helpful advice.
27 D. Clark, I. Woolsey, S. Robinson, K. Laing and J. Wingeld,
Inorg. Chem., 1977, 16, 1201–1206.
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