Search for: All records

Four unsaturated poly(carbooligosilane)s (P1–P4) were prepared via acyclic diene metathesis polycondensation of new oligosilane diene monomers (1–4). These novel polymers with varying main-chain Si incorporation have high trans internal olefin stereochemistry (ca. 80%) and molecular weights (9500–21,700 g mol–1). Postpolymerization epoxidation converted all alkene moieties to epoxides and rendered the polymers (P5–P8) more electrophilic, which allowed for single-molecule force spectroscopy studies via a modified atomic force microscope setup with a silicon tip and cantilever. The single-chain elasticity of the polycarbooligosilanes decreased with increasing numbers of Si–Si bonds, a finding reproduced by quantum chemical calculations. 

The cis- and trans-isomers of a silacycloheptene were selectively synthesized by the alkylation of a silyl dianion, a novel approach to strained cycloalkenes. The trans-silacycloheptene (trans-SiCH) was significantly more strained than the cis isomer, as predicted by quantum chemical calculations and confirmed by crystallographic signatures of a twisted alkene. Each isomer exhibited distinct reactivity toward ring-opening metathesis polymerization (ROMP), where only trans-SiCH afforded high-molar-mass polymer under enthalpy-driven ROMP. Hypothesizing that the introduction of silicon might result in increased molecular compliance at large extensions, we compared poly(trans-SiCH) to organic polymers by single-molecule force spectroscopy (SMFS). Force-extension curves from SMFS showed that poly(trans-SiCH) is more easily overstretched than two carbon-based analogues, polycyclooctene and polybutadiene, with stretching constants that agree well with the results of computational simulations. 

The addition of non‐benzenoid quinones, acenapthenequinone or aceanthrenequinone, to the 9‐carbene‐9‐borafluorene monoanion (1) affords the first examples of dianionic 10‐membered bora‐crown ethers (2–5), which are characterized by multi‐nuclear NMR spectroscopy (¹H,¹³C,¹¹B), X‐ray crystallography, elemental analysis, and UV/Vis spectroscopy. These tetraoxadiborecines have distinct absorption profiles based on the positioning of the alkali metal cations. When compound4, which has a vacant C₄B₂O₄cavity, is reacted with sodium tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate, a color change from purple to orange serves as a visual indicator of metal binding to the central ring, whereby the Na⁺ion coordinates to four oxygen atoms. A detailed theoretical analysis of the calculated reaction energetics is provided to gain insight into the reaction mechanism for the formation of2–5. These data, and the electronic structures of proposed intermediates, indicate that the reaction proceeds via a boron enolate intermediate.

 

The addition of non‐benzenoid quinones, acenapthenequinone or aceanthrenequinone, to the 9‐carbene‐9‐borafluorene monoanion (1) affords the first examples of dianionic 10‐membered bora‐crown ethers (2–5), which are characterized by multi‐nuclear NMR spectroscopy (¹H,¹³C,¹¹B), X‐ray crystallography, elemental analysis, and UV/Vis spectroscopy. These tetraoxadiborecines have distinct absorption profiles based on the positioning of the alkali metal cations. When compound4, which has a vacant C₄B₂O₄cavity, is reacted with sodium tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate, a color change from purple to orange serves as a visual indicator of metal binding to the central ring, whereby the Na⁺ion coordinates to four oxygen atoms. A detailed theoretical analysis of the calculated reaction energetics is provided to gain insight into the reaction mechanism for the formation of2–5. These data, and the electronic structures of proposed intermediates, indicate that the reaction proceeds via a boron enolate intermediate.

 

Borepin, a 7‐membered boron‐containing heterocycle, has become an emerging molecular platform for the development of new materials and optoelectronics. While electron‐deficient borepins are well‐established, reduced electron‐rich species have remained elusive. Herein we report the first isolable, crystalline borepin radical (2 a,2 b) and anion (3 a,3 b) complexes, which have been synthesized by potassium graphite (KC₈) reduction of cyclic(alkyl)(amino) carbene‐dibenzo[b,d]borepin precursors. Borepin radicals and anions have been characterized by EPR or NMR, elemental analysis, X‐ray crystallography, and cyclic voltammetry. In addition, the bonding features have been investigated computationally using density functional theory.

 

Borepin, a 7‐membered boron‐containing heterocycle, has become an emerging molecular platform for the development of new materials and optoelectronics. While electron‐deficient borepins are well‐established, reduced electron‐rich species have remained elusive. Herein we report the first isolable, crystalline borepin radical (2 a,2 b) and anion (3 a,3 b) complexes, which have been synthesized by potassium graphite (KC₈) reduction of cyclic(alkyl)(amino) carbene‐dibenzo[b,d]borepin precursors. Borepin radicals and anions have been characterized by EPR or NMR, elemental analysis, X‐ray crystallography, and cyclic voltammetry. In addition, the bonding features have been investigated computationally using density functional theory.