Incorporation of Group 13 Elements into Polymers

High Molar Mass Poly(alkylphosphinoboranes) via Iron-Catalyzed Dehydropolymerization

“…After 48 h, full conversion to [tBuPH−BH 2 ] n was detected by 11 B NMR (δ = −38.6 ppm) and 31 P NMR (δ = −19.7 ppm) spectroscopy, and the broad signals detected were in accordance with the material prepared previously via the thermal-induced polymerization of tBuPHBH 2 •NMe 3 . 48 Surprisingly, based on the results of our brief previous study, 48 we found that the major fraction of the [tBuPH−BH 2 ] n polymer isolated was of high molar mass (M n = 31,600 g mol −1 , D̵ = 1.49) based on gel permeation chromatography (GPC) analysis with tetrahydrofuran (THF) (0.1 w/w % nBu 4 NBr) as an elution solvent (Figure S5).…”

“…57 Here, we have synthesized iPrPH S1) and were comparable to other phosphine−borane adducts that have been previously described. 34,58 For example, the 11 B NMR spectra each displayed a doublet of quartets at −44.6 ppm for iPrPH 2 •BH 3 and −45.0 ppm for 1-AdPH 2 •BH 3 , and the 31 P NMR spectra each displayed a broad triplet at −26.5 ppm for iPrPH 2 •BH 3 and −14.2 ppm for 1-AdPH 2 •BH 3 (see Supporting Information, Section 3). The molecular structure of 1-AdPH 2 •BH 3 was determined by single-crystal X-ray diffraction, where crystals were obtained from an npentane solution at −40 °C (Table S2, Figure 3).…”

“…Inorganic macromolecules containing p-block elements are of increasing interest as new materials with properties that can show key differences from those of hydrocarbon-based polymers. − For example, polymers that feature boron in the main chain have attracted attention as precursors to high-performance ceramic materials and as optoelectronic and sensory materials. − Catalytic dehydrocoupling of primary amine–borane adducts RNH 2 ·BH 3 , where environmentally benign molecular dihydrogen is the only byproduct, − has been developed as a route to high molar mass polyaminoboranes [RNH–BH 2 ] n , which are isoelectronic inorganic analogues of polyolefins. These materials possess interesting potential applications as piezoelectrics , and as precursors to BN ceramics. − Analogous high molar mass aryl P-substituted polyphosphinoboranes [RPH–BH 2 ] n (R = Ph or para-substituted aryl) were initially prepared through catalytic P–B bond formation via dehydropolymerization reaction involving primary phosphine–boranes RPH 2 ·BH 3 assisted by Rh-based precatalysts at 90–130 °C under melt conditions. − The temperature of dehydropolymerization can be lowered to 60 °C when activated adducts substituted with electron-withdrawing perfluorinated aryl groups are used .…”

Anionic Polymerization of Para-Diethynylbenzene: Synthesis of a Strictly Linear Polymer

“…The reaction of decaborane with low molecular weight acetylenes is well known [ 62 ]. This reaction was used to create polymer carborane-containing clusters using poly-conjugated ethynylene-containing polymers [ 63 , 64 ], as well as for the creation of carboranes in the side hangers of polystyrene [ 63 ]. The synthesis of various boron-containing polymers is due to the creation of luminescent, electroactive, sensory, thermo-, and fire-resistant materials [ 63 , 64 , 65 ].…”

“…This reaction was used to create polymer carborane-containing clusters using poly-conjugated ethynylene-containing polymers [ 63 , 64 ], as well as for the creation of carboranes in the side hangers of polystyrene [ 63 ]. The synthesis of various boron-containing polymers is due to the creation of luminescent, electroactive, sensory, thermo-, and fire-resistant materials [ 63 , 64 , 65 ]. The reaction of decaborane modification of a polymer containing –C≡CH groups and synthesized in the presence of a Ni(C 5 H 7 O 2 ) 2 /Ph 3 P complex is described [ 66 ].…”