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. 2018 Oct 8;8(60):34491-34504.
doi: 10.1039/c8ra05969a. eCollection 2018 Oct 4.

Solventless, selective and catalytic oxidation of primary, secondary and benzylic alcohols by a Merrifield resin supported molybdenum(vi) complex with H2O2 as an oxidant

Jeena Jyoti Boruah  1   2 , Siva Prasad Das  1
Affiliations

Solventless, selective and catalytic oxidation of primary, secondary and benzylic alcohols by a Merrifield resin supported molybdenum(vi) complex with H2O2 as an oxidant

Jeena Jyoti Boruah et al. RSC Adv. .

Abstract

Here, we have described the synthesis, characterization and catalytic activity of a dioxo-molybdenum(vi) complex supported on functionalized Merrifield resin (MR-SB-Mo). The functionalization of Merrifield resin (MR) was achieved in two-steps viz. carbonylation (MR-C) and Schiff base formation (MR-SB). The compounds, MR-C, MR-SB and MR-SB-Mo, were characterized at each step of the synthesis by elemental, SEM, EDX, thermal, BET and different spectroscopic analysis. The catalyst, MR-SB-Mo, efficiently and selectively oxidized a wide variety of alcohols to aldehydes or ketones using 30% H2O2 as an oxidant with reasonably good TOF (660 h-1 in case of benzyl alcohol). The catalyst acted heterogeneously under solventless reaction conditions and did not lead to over oxidized products under optimized conditions. The catalyst afforded regeneration and can be reused for at least five reaction cycles without loss of efficiency and product selectivity. A reaction mechanism for the catalytic activity of MR-SB-Mo was proposed and a probable reactive intermediate species isolated.

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Conflict of interest statement

There are no conflicts of interest to declare.

Figures

Scheme 1
Scheme 1. Synthesis of MR-SB-Mo. “” represents polymeric support.
Fig. 1
Fig. 1. Scanning electron micrographs of (a) MR, (b) MR-C, (c) MR-SB, and (d) MR-SB-Mo. EDX spectra of (e) MR-SB-Mo.
Fig. 2
Fig. 2. The XRD patterns of (a) MR, (b) MR-C, (c) MR-SB and (d) MR-SB-Mo.
Fig. 3
Fig. 3. XPS Mo (3d3/2) and Mo (3d5/2) spectra of (a) MR-SB-Mo and (b) MR-SB-Mo after the 5th reaction cycle.
Fig. 4
Fig. 4. FTIR spectra for (a) MR, (b) MR-C, (c) MR-SB, (d) MR-SB-Mo, and (e) MR-SB-Mo after 5th reaction cycle.
Fig. 5
Fig. 5. Raman spectrum for MR-SB-Mo.
Fig. 6
Fig. 6. The TGA thermograms of MR (black), MR-C (red), MR-SB (blue), and MR-SB-Mo (green).
Scheme 2
Scheme 2. Optimum reaction condition for oxidation of alcohol catalyzed by MR-SB-Mo using 30% H2O2 as oxidant.
Fig. 7
Fig. 7. Catalyst recycling.
Scheme 3
Scheme 3. Proposed reaction mechanism for oxidation of alcohols using benzyl alcohol as representative. “NN” stands for the nitrogen coordination site for imine and pyridine group and “” represents polymeric support.
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