Polymers from Bioderived Resources: Synthesis of Poly(silylether)s from Furan Derivatives Catalyzed by a Salen–Mn(V) Complex

Abstract

Synthesis of degradable polymers from renewable resources has been a promising way to replace nonrenewable fossil fuel derived polymers motivated by environmental sustainability. Poly­(silylether)­s (PSEs) are a specific type of environmentally degradable polymer with many potential applications. A series of PSEs have been synthesized (M n up to 25 000 g/mol) from biorenewable feedstocks, such as 5-hydroxymethylfurfural and its derivatives 2,5-bis­(hydroxymethyl)­furan, 2,5-diformylfuran, and 5,5′-[oxybis­(methylene)]­di­(2-furaldehyde). The polymerization reactions employ a versatile, air-stable manganese salen complex, which catalyzes both the dehydrogenative cross-coupling of hydroxyls with hydrosilanes and the hydrosilylation of carbonyls. The chemical and thermal characterization of PSEs was carried out by 1H NMR, 13C NMR, Fourier transform infrared spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis.

A β-diketiminate manganese catalyst for alkene hydrosilylation: substrate scope, silicone preparation, and mechanistic insight

“…4 , P-2 ). It should be noted that Du and co-workers have recently described the synthesis of silicones by way of Mn-mediated carbonyl hydrosilylation and dehydrogenative alcohol silylation; 34 however, P-1 and P-2 are believed to be the first silicones featuring non-hydrolysable Si–C bonds prepared via Mn catalysis.…”

Manganese‐Catalysed Dehydrogenative Coupling – An Overview

“…Recently the same group has judiciously used this methodology in the synthesis of biodegradable poly(silyl ether)s from renewable 2,5‐bis(hydroxymethyl)furan (HMF) and its derivatives (Scheme ) …”

Biological and catalytic potential of sustainable low and high valent metal-Schiff base sulfonate salicylidene pincer complexes

“…73 The higher stability of high valent metal complexes could resist the reduction step in order to prepare the active catalyst of the low oxidation state in the catalytic cycle. 38,74 Although, Mncomplexes presented in high oxidation state Mn(V)-Salen as an effective catalyst for polymerization of furan derivatives awarding poly(silylether)s, 75 the high valent M-complexes (UO 2 Saln, MoO 2 Saln, VOSaln and VOSaln-Ph complexes) as catalysts for such coupling systems did not promote the catalytic process. Most probably the low efficiency of UO 2 Saln, MoO 2 Saln, VOSaln and VOSaln-Ph complexes could be due to the doubly bonded oxygen to the metal ion (Mo 6+ , U 6+ and V 4+ ion), forming the high stable oxidation state of those metal ions, preventing its reduction to lower oxidation state in such crosscoupling mechanisms.…”