Going beyond Red with a Tri- and Tetracoordinate Boron Conjugate: Intriguing Near-IR Optical Properties and Applications in Anion Sensing

The design and synthesis of a new tri- and tetracoordinate boron conjugate is reported. The conjugate shows broad near-IR emission (∼625–850 nm) and is found to be a selective colorimetric and ratiometric sensor for fluoride ions

Photochemically and Thermally Generated BN-Doped Borafluorenate Heterocycles via Intramolecular Staudinger-Type Reactions

No description supplied.</p

Insertion Reaction of Me₃SiN₃ with Bis(germylene)

Herein, we describe the redox reaction of bis­(germylene) PhC­(NtBu)2Ge–Ge­(NtBu)2CPh with different equivalents of Me3SiN3 affording two distinct products. The reaction of Me3SiN3 with bis-germylene in a 1:1 molar ratio results in compound 1 at −78 °C; however, treatment of bis-germylene with a 2.1 equiv of Me3SiN3 at room temperature results in compound 2. The formation of 1 and 2 can be rationalized by two successive 3 + 1 cycloadditions of Me3SiN3 with the germanium center of bis­(germylene) and N2 elimination. All of the compounds are well-characterized by various spectroscopic techniques and single-crystal X-ray structural analyses. Density functional theory (DFT) calculations suggest that compound 2 has a dicoordinated nitrogen atom, which is stabilized by hyperconjugative interactions, resulting in pseudo-germylimine moiety. However, the dicoordinated nitrogen atom shows high basicity as indicated by proton affinity values. These are rare examples of isolated products that show insertion as well as simultaneous redox properties of bis­(germylene)

Isolation of Transient Acyclic Germanium(I) Radicals Stabilized by Cyclic Alkyl(amino) Carbenes

Despite the notable progress in the stabilization of main group radicals by NHCs and cAACs, no germanium radicals have been isolated so far due to synthetic challenges. Stabilization of neutral [:EIR]• (E = Si, Ge) radicals is an uphill task, as these reactive transient species are highly susceptible to dimerization. Herein, we report the synthesis of acyclic neutral germanium­(I) radicals Cy-cAAC:GeN­(SiMe3)­Dip (1) and Me-cAAC:GeN­(SiPh3)­Mes (2) obtained by the reduction of [Ar­(SiR3)­NGeCl3] with KC8 in the presence of cAAC. Compounds 1 and 2 are well characterized by single crystal X-ray structural analysis, cyclic voltammetry, and EPR spectroscopy. Furthermore, the structure and bonding of compounds 1 and 2 have been investigated by theoretical methods

Isolation of Transient Acyclic Germanium(I) Radicals Stabilized by Cyclic Alkyl(amino) Carbenes

Despite the notable progress in the stabilization of main group radicals by NHCs and cAACs, no germanium radicals have been isolated so far due to synthetic challenges. Stabilization of neutral [:EIR]• (E = Si, Ge) radicals is an uphill task, as these reactive transient species are highly susceptible to dimerization. Herein, we report the synthesis of acyclic neutral germanium­(I) radicals Cy-cAAC:GeN­(SiMe3)­Dip (1) and Me-cAAC:GeN­(SiPh3)­Mes (2) obtained by the reduction of [Ar­(SiR3)­NGeCl3] with KC8 in the presence of cAAC. Compounds 1 and 2 are well characterized by single crystal X-ray structural analysis, cyclic voltammetry, and EPR spectroscopy. Furthermore, the structure and bonding of compounds 1 and 2 have been investigated by theoretical methods

Isolation of Transient Acyclic Germanium(I) Radicals Stabilized by Cyclic Alkyl(amino) Carbenes

Despite the notable progress in the stabilization of main group radicals by NHCs and cAACs, no germanium radicals have been isolated so far due to synthetic challenges. Stabilization of neutral [:EIR]• (E = Si, Ge) radicals is an uphill task, as these reactive transient species are highly susceptible to dimerization. Herein, we report the synthesis of acyclic neutral germanium­(I) radicals Cy-cAAC:GeN­(SiMe3)­Dip (1) and Me-cAAC:GeN­(SiPh3)­Mes (2) obtained by the reduction of [Ar­(SiR3)­NGeCl3] with KC8 in the presence of cAAC. Compounds 1 and 2 are well characterized by single crystal X-ray structural analysis, cyclic voltammetry, and EPR spectroscopy. Furthermore, the structure and bonding of compounds 1 and 2 have been investigated by theoretical methods