Metal‐Free Hydrosilylation Polymerization by Borane Catalyst

Abstract

The first example of metal-free hydrosilylation polymerization between dienes and disilanes is developed by using aborane catalyst, B(C 6 F 5 ) 3 to replace precious transitionmetal-based systems.U nder the easy-to-handle and mild conditions,astep-growth polymerization of two readily available diene and disilane units was achieved with high degrees of polymerization. Various combinations of dienes and disilanes produced polycarbosilanes with ab road range of structures and properties.

Fifty Years of Hydrosilylation in Polymer Science: A Review of Current Trends of Low-Cost Transition-Metal and Metal-Free Catalysts, Non-Thermally Triggered Hydrosilylation Reactions, and Industrial Applications

“…Chang and coworkers reported the metal-free hydrosilylation polymerization of dienes and with disilanes using the tris(pentafluorophenyl)borane catalyst [54]. Their method provided polymers with high polymerization degrees; various poly(carbosilane)s could be produced with a broad range of structures and properties.…”

Cobalt‐Catalyzed Regiodivergent Double Hydrosilylation of Arylacetylenes

“…Accordingly, apart from some traditional stoichiometric reactions, [4] several catalytic methods have been developed, such as carbene insertion into Si−Si bonds, [5] double C(sp 3 )−Si coupling of dibromides, [6] disilylation of alkenes, [7] hydrosilylation of vinylsilanes, [8] C−H silylation, [9] etc [10] . Most of these methods only afford bis‐silyl products without Si−H bonds, which could restrict their downstream modifications [11] and further application in hydrosilylation polymerization [1e, 9, 11g] . Besides, reliable and economic synthetic methods to access structural‐versatile bis(silane)s are still limited, making the application exploration of bis‐silyl compounds limited.…”

Nickel‐Catalyzed Reductive C(sp2)−Si Coupling of Chlorohydrosilanes via Si−Cl Cleavage

“…The use of ditriflates afforded good yields of bis(hydrosilyl)benzenes 3 w and 3 x, which have found applications in polymer chemistry. [24] In addition to triflates, aryl bromides were also suitable, thereby providing a substrate scope complementary to triflates (Table 2). Alkenylhydrosilanes are essential building blocks that are widely applied in organic synthesis.…”