Poly(cyclosilane) Postpolymerization Hydrosilylation

Coschigano, Marissa G.; Gregory, Sydney L.; Catazaro, Jonathan; Rossini, Aaron J.; Klausen, Rebekka S.

doi:10.1021/acs.macromol.3c02110

Poly(cyclosilane) Postpolymerization Hydrosilylation

Journal Article · Fri Apr 19 00:00:00 EDT 2024 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.3c02110· OSTI ID:2338167

Coschigano, Marissa G. ^[1]; Gregory, Sydney L. ^[2]; Catazaro, Jonathan ^[2]; ^[3]; ^[2]

Johns Hopkins Univ., Baltimore, MD (United States); Johns Hopkins University
Johns Hopkins Univ., Baltimore, MD (United States)
Ames Lab., and Iowa State Univ., Ames, IA (United States)

Postpolymerization functionalization is a key strategy in the diversification of polymeric materials for the conferral of tailored properties. Poly(cyclosilane)s are structurally complex polymers with an all-silicon backbone, featuring a periodic array of hydrido (Si–H) side chains that are potentially suitable for postpolymerization functionalization via hydrosilylation. At the same time, classical methods for hydrosilylation employing Pt- or Pd-based catalysts can result in Si–Si bond scission. In this work, we demonstrate borane-catalyzed hydrosilylation reactions between α-olefins and small molecules or three distinct poly(cyclosilane) architectures. We investigate chemoselectivity for end group versus internal Si–H groups and find that ²⁹Si cross-polarization magic angle spinning can provide insight on site-selectivity in the functionalization of a complex poly(cyclosilane). Furthermore, we show that postpolymerization hydrosilylation, converting oxidatively sensitive Si–H groups to Si–alkyl chains, modulates solubility and physical characteristics, optical properties, pyrolytic reactivity, and air sensitivity.

View Accepted Manuscript (DOE)

Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0020681

OSTI ID:: 2338167

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 9 Vol. 57; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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