RESEARCH PAPER
CHINESE JOURNAL OF CATALYSIS
Volume 32, Issue 10, 2011
Online English edition of the Chinese language journal
Cite this article as: Chin. J. Catal., 2011, 32: 1597–1603.
Received 9 May 2011. Accepted 30 July 2011.
*Corresponding author. Tel: +91-1881-242175; Fax: +91-1881-223395; E-mail: rajendra@iitrpr.ac.in
The authors thank the Ministry of Human Resource and Development, New Delhi and Director, IIT Ropar for financial assistance.
Copyright © 2011, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier BV. All rights reserved.
DOI: 10.1016/S1872-2067(10)60266-5
Catalytic Activity of Dual Metal Cyanide Complex in
Multi-Component Coupling Reactions
Anaswara RAVINDRAN, Rajendra SRIVASTAVA*
Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar 140001, India
Abstract: Several dual metal cyanide catalysts were prepared from potassium ferrocyanide, metal chloride (where metal = Zn
2+
, Mn
2+
, Ni
2+
,
Co
2+
, and Fe
2+
), t-butanol (complexing agent) and PEG-4000 (co-complexing agent). The catalysts were characterized by elemental analysis
(CHN and X-ray fluorescence), X-ray diffraction, N
2
adsorption-desorption, scanning electron microscopy, Fourier-transform infrared
spectroscopy, and UV-Visible spectroscopy. The dual metal cyanide catalysts were used in several acid catalyzed multi-component coupling
reactions for the synthesis of pharmaceutically important organic derivatives. In all these reactions, the Fe-Fe containing dual metal cyanide
catalyst was the best catalyst. The catalysts can be recycled without loss in catalytic activity. The advantage of this method is the use of mild,
efficient and reusable catalysts for various reactions, which makes them candidates for commercial use.
Key words: dual metal cyanide; multi-component coupling reaction; acid catalyst
Dual metal cyanide (DMC) catalysts are a class of molecular
salts comprising a metal-cyanide crystalline framework with
two different metal centers. They have the general formula
M
1
u
[M
2
(CN)
6
]
v
·yL·zH
2
O (where M
1
= Zn; M
2
= Co, Fe etc.; L =
organic complexing agent) [1–4]. DMC catalysts possess zeo-
lite-like cage structures [5], and have gained considerable
attention for their interesting magnetic, electrochromic, mag-
neto-optic, photomagnetic, and nanomagnetic properties [6].
DMC catalysts are insoluble in organic solvents, acids, and
even in aqua regia. They are usually prepared by the precipi-
tation reaction of an aqueous solution of a water-soluble metal
salt (M
u
1
X
w
), metal cyanide potassium salt (K
a
[M(CN)
n
]
v
), and
a water-soluble organic complexing agent (L).
DMC catalysts were discovered in the 1960’s [7] and were
found to have significant catalytic activity in various reactions,
in particular in polymerization reactions [8–14]. DMC com-
plexes find extensive applications in the ring opening polym-
erization of epoxides [1–4]. DMC catalysts can be used to
produce polyether, polyester, and poly (ether ester) polyols
[8–11]. Environmentally friendly synthesis of biodegradable
polycarbonates was realized using DMC catalysts by the co-
polymerization of epoxide with CO
2
[12,13]. They have been
relatively well investigated with respect to their activity using
different preparation routes and operating conditions [12,14].
The recent literature suggest that they can be effectively util-
ized in esterification and transesterification reactions for the
production of organic carbonates and biodiesel [15,16].
Multi-component reactions are a powerful and useful syn-
thetic tool to produce complex molecules from simple pre-
cursors by a one-pot procedure [17–19]. In this procedure,
there is no need to isolate any intermediate, and there is re-
duction in the reaction time and savings in both energy and raw
materials. Therefore, the design of novel multi-component
reactions has attracted a great deal of attention from research
groups working in the field of medicinal chemistry, drug dis-
covery, and material science.
To utilize DMC in chemical synthesis, Fe-Zn based DMC
catalysts have been prepared by varying several synthesis
parameters [15,16]. However, the influence on reactivity of
changing the metal ions in the DMC has not been explored. The
objective of this study is to prepare a variety of DMC catalysts
and assess their catalytic activity in chemical synthesis. A
variety of Fe-M-containing DMC catalysts (M = Fe, Mn, Co,
Ni, and Zn) were prepared (with all other synthesis parameters
the same). Their catalytic activities were assessed using
multi-component coupling reactions in the synthesis of phar-