Abstract Ruthenium(II)‐catalyzed meta ‐selective C−H (di)fluoromethylation was accomplished by phosphine and carboxylate cooperation. The remote functionalization characterized ample substrate scope, thereby setting the stage for ‐(di)fluoromethylation through facile cleavage.

Abstract Ruthenium(II)‐catalyzed meta ‐selective C−H (di)fluoromethylation was accomplished by phosphine and carboxylate cooperation. The remote functionalization characterized ample substrate scope, thereby setting the stage for ‐(di)fluoromethylation through facile cleavage.

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

Herein, we report the stabilization of nitrene reagents as source a nitrogen atom to synthesize nitrogen-incorporated R

Hirshfeld atom refinement (HAR) is an X-ray diffraction method that, in numerous publications, has been shown to give H-atom bond lengths close agreement with neutron derived values. Presented here a first evaluation of approach using densities from projector augmented wave (PAW) three-dimensional periodic boundary conditions for HAR. The results show improvement over refinements that neglect the crystal environment or treat it classically, while being on par non-periodic approximations...

Electron-deficient, anti-aromatic 2,5-disilyl boroles are shown to be a flexibly adaptive molecular platform with regards SiMe3 mobility in their reaction the nucleophilic donor-stabilised precursor dichloro silylene SiCl2(IDipp). Depending on substitution pattern, selective formation of two fundamentally different products rivalling pathways is achieved. Formal addition dichlorosilylene gives 5,5-dichloro-5-sila-6-borabicyclo[2.1.1]hex-2-ene derivatives. Under kinetically controlled...

The reduction of TipMCl3 (Tip=2,4,6-triisopropylphenyl) (M=Si, Ge) with KC8 in the presence cyclic alkyl(amino) carbene (cAAC) afforded acyclic silanylidene and germanylidene anions form potassium salt [K(cAAC)MTip]2 (M=Si (1); Ge (2)). are valence-isoelectronic to well-studied phosphinidene a new class Group 14. Compounds 1 2 were isolated well characterized by NMR single-crystal X-ray structure analysis. Furthermore, bonding compounds was investigated computational methods.

The MetalJet X-ray source provides indium K α radiation with a wavelength even shorter than Ag radiation. This paper reports on problematic spectral impurities and presents possible countermeasures so that collection of data excellent quality up to high resolution is possible. It demonstrated these can be used in the refinement multipole model, results which are for topological analysis assess bonding situation sulfur ylide compound.

Abstract The pentaaryl borole (Ph*C) 4 BXyl F [Ph*=3,5‐ t Bu 2 (C 6 H 3 ); Xyl =3,5‐(CF ) )] reacts with low‐valent Group 13 precursors AlCp* and GaCp* by two divergent routes. In the case of [AlCp*] , as an oxidising agent accepts electrons. Structural, spectroscopic, computational analysis resulting unprecedented neutral η 5 ‐Cp*,η ‐[(Ph*C) ] complex Al III revealed a strong, ionic bonding interaction. formation heteroleptic borole‐cyclopentadienyl “aluminocene” leads to significant...

Three positional isomers of thiophosphoranyl anthracene were synthesized and their photophysical properties investigated. By varying the position substituents, blue, green yellow solid-state fluorescence with differences in emission wavelength over 100 nm, assigned to intra- intermolecular effects, could be established.

We describe the facile and selective one-pot synthetic route to silylene-aluminum silylene-gallium adducts, in which one silicon atom of bis(silylene) functions as a Lewis base under adduct formation with acid.

Small robust organic molecules showing solid-state luminescence are promising candidates for optoelectronic materials. Herein, we investigate a series of diphenylphosphanyl anthracenes [9-PPh2 -10-R-(C14 H8 )] and their sulfur oxidised analogues. The oxidation causes drastic changes in the molecular structure as new orientation bulky (S)PPh2 substituent induces strong butterfly bent anthracene core, which triggers bathochromic shift resulting green fluorescence. As emission properties change...

The MetalJet source makes available new Kα radiation wavelengths for use in X-ray diffraction experiments. purpose of this paper is to demonstrate the application indium independent-atom model refinement, as well approaches using aspherical atomic form factors. results vary greatly depending on detector employed, energy cut-off Eiger2 CdTe provides a solution unique contamination problem In radiation, which Photon III cannot provide.

The sterically encumbered cyclopentadienyl ligand 1,2,4-(Me₃C)₃C₅H₂ (Cp′′′) effectively stabilizes the main group metals of Al, Ga, In, Ge and Sn with σ- or π-bonds.

Abstract The reduction of an N ‐heterocyclic carbene (1,3‐diisopropyl‐4,5‐dimethylimidazolin‐2‐ylidene, I i Pr ) adduct dichloro( ortho ‐bromophenyl)borane by tert ‐butyl lithium at low temperature yields the A parent benzoborirene, a highly strained boron‐containing bicyclic compound. is unstable room and dimerizes to bis‐I 9,10‐dihydro‐9,10‐diboraanthracene, characterized single‐crystal X‐ray crystallography.

Herein, we describe the redox reaction of bis(germylene) PhC(NtBu)2Ge-Ge(NtBu)2CPh with different equivalents Me3SiN3 affording two distinct products. The bis-germylene in a 1:1 molar ratio results compound 1 at -78 °C; however, treatment 2.1 equiv room temperature 2. formation and 2 can be rationalized by successive 3 + cycloadditions germanium center N2 elimination. All compounds are well-characterized various spectroscopic techniques single-crystal X-ray structural analyses. Density...

Abstract The reduction of TipMCl 3 (Tip=2,4,6‐triisopropylphenyl) (M=Si, Ge) with KC 8 in the presence cyclic alkyl(amino) carbene (cAAC) afforded acyclic silanylidene and germanylidene anions form potassium salt [K(cAAC)MTip] 2 (M=Si ( 1 ); Ge )). are valence‐isoelectronic to well‐studied phosphinidene a new class Group 14. Compounds were isolated well characterized by NMR single‐crystal X‐ray structure analysis. Furthermore, bonding compounds was investigated computational methods.

Irradiation of dibenzyl diselenide BnSeSeBn with X-ray or UV-light cleaves the Se-C and Se-Se bonds, inducing stable metastable radical states. They are inevitably important to all natural life sciences. Structural changes due X-ray-induced bond-cleavage could be pin-pointed in various high-resolution diffraction experiments for first time. Extended DFT methods were applied characterize solid-state structure support refinement observed residuals as contributions from BnSeSe⋅ species. The...

Abstract Bislang galt die Struktur des Decamethylsilicocens Cp* 2 Si mit einem gewinkelten und linearen Molekül in derselben Elementarzelle als Ausnahme unter den ansonsten ausschließlich schweren Homologen E E=Ge, Sn, Pb. Hier stellen wir Rätsels Lösung einer Tieftemperaturphase vor, der alle drei symmetrieunabhängigen Moleküle gewinkelte Konformation einnehmen. Der reversible Phasendurchgang geschieht im Temperaturbereich zwischen 80 130 K bietet eine rationale Erklärung auf Grundlage...

Abstract Herein, we report the stabilization of nitrene reagents as source a nitrogen atom to synthesize nitrogen‐incorporated R 1 LSi‐N←SiLR 2 ( ) [L=PhC(N t Bu) ; =NTMS , =NTMS]. Compound is synthesized by reacting LSi(I)‐Si I L with 3.1 equivalents Me 3 SiN at low temperature afford triene‐like structural framework. Whereas reaction 2.1 room produced silaimine central four‐membered Si N ring which accompanied silylene LSi and cleaved fragment. further reacts AgOTf yield compound shows...

Abstract Das Pentaarylborol (Ph*C) 4 BXyl F [Ph*=3,5‐ t Bu 2 (C 6 H 3 ); Xyl =3,5‐(CF ) )] reagiert mit den niedervalenten Cyclopentadienylverbindungen der Gruppe 13 E(I)Cp* (E=Al, Ga). Gegenüber [AlCp*] wirkt das Borol als Oxidationsmittel und nimmt zwei Elektronen auf. Dies führt zum bisher unbekannten, neutralen η 5 ‐Cp*,η ‐[(Ph*C) ]‐Komplex des Al III , strukturell, spektroskopisch computerchemisch untersucht wurde. Die Bildung heteroleptischen Borol‐Cyclopentadienyl‐“Aluminocens” zu...

Abstract Irradiation of dibenzyl diselenide BnSeSeBn with X‐ray or UV‐light cleaves the Se−C and Se−Se bonds, inducing stable metastable radical states. They are inevitably important to all natural life sciences. Structural changes due X‐ray‐induced bond‐cleavage could be pin‐pointed in various high‐resolution diffraction experiments for first time. Extended DFT methods were applied characterize solid‐state structure support refinement observed residuals as contributions from BnSeSe⋅...

The solid-state structure of decamethylsilicocene Cp*2 Si with a bent and linear molecule in the same unit cell was so far considered an exception relation to structures its all-bent heavier analogues E E=Ge, Sn, Pb. Here, we present solution this conundrum by reporting low-temperature phase, where all three symmetrically independent molecules are formation. This reversible enantiotropic phase transition occurs temperature range between 80 K 130 provides rationale for unexpected based...