Zinc‐Catalyzed Hydrosilylation Copolymerization of Aromatic Dialdehydes with Diphenylsilane

Abstract

The hydrosilylation reaction of diphenylsilane and phthalaldehyde is catalyzed by heteroscorpionate zinc hydride complex LZnH (1, L = ( Pz) CP(Ph) NPh, Pz = 3,5-dimethylpyrazolyl). Both terephthalaldehyde (tPAA) and isophthalaldehyde (iPAA) affords linear polymer; however, when PAA is used, a seven-membered cyclic silyl ether is formed. These products are characterized by H and C NMR spectra. Other properties of polymers are determined by gel permeation chromatography (GPC)-multiangle laser-light scattering, differential scanning calorimetry, and thermogravimetry.

Molecular Main Group Metal Hydrides

“…For example, the catalyst combination 397 /B­(C 6 F 5 ) 3 promoted the tandem reduction and copolymerization of 5-hydroxyfurfural with dihydrosilanes (1 mol % cocatalyst loading) to yield the polymers shown in eq 57 , with polymer number-average molecular weights ( M n ) of 8-20 kDa reported . A related procedure was used by the same group to form the copolymer [-OCH 2 – p -C 6 H 4 –CH 2 O-SiPh 2 -] n with 397 as the catalyst …”

Metal-Free Synthesis of Poly(silyl ether)s under Ambient Conditions

“…In addressing these challenges, our attention was directed toward hydrosilylation reactions involving the addition of silicon hydrides across unsaturated bonds as an attractive approach toward novel poly­(silyl ether)­s. − Pioneering work by Weber illustrated that poly­(silyl ether)­s can be prepared by hydrosilylation coupling catalyzed by transition metal complexes, including ruthenium and rhodium; − however, the reported processes suffer from harsh reaction conditions and side reactions as well as the high cost/low abundance of Ru/Rh catalysts (Scheme ). Because of these drawbacks and an increasing interest in mild, metal-free methods for the synthesis of functional polymers, we examined the hydrosilylation of carbonyl groups catalyzed by tris­(pentafluoro­phenyl)­borane (B­(C 6 F 5 ) 3 ) in detail.…”

Step‐Growth Coordination Polymerization of 5‐Hydroxymethyl Furfural with Dihydrosilanes: Synergistic Catalysis Using Heteroscopionate Zinc Hydride and B(C6F5)3

“…The zwiteronic heteroscopionate zinc hydrido complex LZnH (L=( Me Pz) 2 CP(Ph) 2 NPh, Me Pz=3,5‐dimethylpyrazolyl) was the first earth‐abundant metal‐based catalyst used for the hydrosilylation polymerization of α,ω‐dialdehydes as reported by us recently . Therefore, LZnH (1 mol %) was used to catalyze the hydrosilylation polymerization of HMF and diphenylsilane (DPS).…”