Zirconium(IV)-catalysed hydrosilylation of organic carbonates and polycarbonates household wastes into alcohol derivatives.

01 February 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The Schwartz’s reagent Cp2Zr(H)Cl is a well known stoichiometric reagent for the reduction of unsaturated organic molecules but it has rarely been used in catalytic transformations. Herein, we describe the reduction of a variety of organic carbonates using the catalyst Cp2Zr(H)Cl in combination with Me(MeO)2SiH (DMMS) as reductant. This method was further applied to the reductive depolymerization of some polycarbonate materials and yielded sylilated alcohols and diols in mild conditions. A significant advantage of this recycling method of polycarbonates is its stability towards the additives contained in household plastics and its ability to selectively depolymerize polycarbonate in a mixture containing a polyester and a polycarbonate. Experimental investigations brought evidences on a mechanism based on the hydrozirconation of the carbonyl fragment, thermal σ C–O bond cleavage, and Zr–OR/Si–H σ-bond metathesis reactions to regenerate the hydride catalyst.

Keywords

organic carbonates
Hydrosilylation
Polycarbonate depolymerization
Plastic
Schwartz reagent
Zirconium hydride
catalysis

Supplementary materials

Title
Description
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Title
Zirconium(IV)-catalyzed hydrosilylation of organic carbonates and polycarbonates household wastes into alcohol derivatives.
Description
Experimental part of the manuscript
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Comment number 1, Juventino Garcia: Mar 21, 2024, 23:31

The introduction contains an inaccurate citation on reference 18 since Cantat´s reports never inspired our work. To his disgrace, he must cite our work, but he can´t properly do so.