Catalytic Conversion of Carbon Dioxide Using Binuclear
Double-Stranded Helicates: Cyclic Carbonate from Epoxides and Diol
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Posted on 2020-06-22 - 13:04
The
construction of sophisticated molecular architectures from
chemical subunits requires careful selection of the spacers, precise
synthetic strategies, and substantial efforts. Here, we report a series
of binuclear double-stranded helicates synthesized from different
combinations of pyridyl hydrazone-based multidentate ligands (H21, H22, H23) by increasing the methylene spacer and transition
metals (Co, Ni, and Zn). The ligands H21 (N′1,N′3-bis((E)-pyridin-2-ylmethylene)malonohydrazide), H22 (N′1,N′4-bis((E)-pyridin-2-ylmethylene)succinohydrazide), and H23 (N′1,N′5-bis((E)-pyridin-2-ylmethylene)glutarohydrazide) and their respective
complexes with Co, Ni, and Zn were obtained. Single-crystal X-ray
diffraction studies of these binuclear metallohelicates confirm the
double-stranded helical structure of the complexes derived from H22. The set of helicates Co-1, Co-2, and Co-3; Ni-1, Ni-2, and Ni-3; and Zn-1, Zn-2, and Zn-3 were investigated for its catalytic activity
in the cyclic carbonate formation reaction. Intriguingly, among the
synthesized catalyst, Co-1 was found to be better in
terms of conversions with the calculated TOF (turnover frequency)
of 128/h. The catalytic performance was significantly improved by
adding 0.2 mmol of tetrabutylammonium bromide by achieving 76% conversion
in 30 min, with the observed TOF of 15,934 h–1/molecule
and 7967 h–1/Co center. The results obtained herein
show that the double-stranded helicates are effective catalysts for
converting both terminal and non-terminal epoxides into their corresponding
cyclic carbonates. The striking feature of this catalytic protocol
lies in demonstrating the catalytic activity for the conversion of
diol to cyclic carbonate, and the detailed kinetic experiments tempted
us to propose a tentative reaction mechanism for this conversion.
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Arunachalam, Rajendran; Chinnaraja, Eswaran; Subramanian, Saravanan; Suresh, Eringathodi; Subramanian, Palani S. (2020). Catalytic Conversion of Carbon Dioxide Using Binuclear
Double-Stranded Helicates: Cyclic Carbonate from Epoxides and Diol. ACS Publications. Collection. https://doi.org/10.1021/acsomega.9b04241