Coordinatively Unsaturated Amidotitanocene Cations with Inverted σ and π Bond Strengths: Controlled Release of Aminyl Radicals and Hydrogenation/Dehydrogenation Catalysis

Cationic amidotitanocene complexes [Cp₂Ti(NPhAr)][B(C₆F₅)₄] (Cp=η⁵-C₅H₅; Ar=phenyl ( 1 a ), p-tolyl ( 1 b ), p-anisyl ( 1 c )) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti−N bond in 1 a–c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a–c undergo photolytic Ti−N cleavage to release Ti(III) species and aminyl radicals ⋅ NPhAr. Reaction of 1 b with H₃BNHMe₂ results in fast homolytic Ti−N cleavage to give [Cp₂Ti(H₃BNHMe₂)][B(C₆F₅)₄] ( 3 ). 1 a–c are highly active precatalysts in olefin hydrogenation and silanes/amines cross-dehydrogenative coupling, whilst 3 efficiently catalyzes amine-borane dehydrogenation. The mechanism of olefin hydrogenation was studied by DFT and the cooperative H₂ activation key step was disclosed using the Activation Strain Model (ASM).     

Alkyne Aminopalladation/Heck and Suzuki Cascades: An Approach to Tetrasubstituted Enamines

Alkyne aminopalladation reactions starting from tosylamides are reported. The emerging vinylic Pd species are converted either in an intramolecular Heck reaction with olefinic units or in an intermolecular Suzuki reaction by using boronic acids exhibiting broad functional group tolerance. Tetra(hetero)substituted tosylated enamines are obtained in a simple one-pot process.     

Understanding mechanisms of drying of a cellulose slurry by magnetic resonance imaging

Cellulose - This study concerns the spatial evolution of the internal components of a macroscopic sample of cellulose slurry during its convective drying. In a first stage, some water is extracted...     

A New Eremophilane Sesquiterpenoid from Ligularia przewalskii

Chemistry of Natural Compounds - A new eremophilane sesquiterpenoid, 3β-acetoxy-6α-angeloyloxy-eremophil-1(10),7(11),8(9)-trien-12,8-olide (1), was isolated from Ligularia przewalskii....     

Triterpenoids with Cytotoxicity from Abelia engleriana

Chemistry of Natural Compounds -     

Analysis and Comparison Constituent of the Essential Oil from Three Different Species of Achillea L. in the Northern Slope of Tianshan Mountains

Moscow University Chemistry Bulletin - The genus Achillea L. (Family: Asteraceae) is a kind of perennial plant, mostly distributed in north western region of China, especially in Tianshan Mountains...     

Development and testing of a Frisch-Grid Ionization Chamber for the measurement of low activity of alpha-particle emitters

Journal of Radioanalytical and Nuclear Chemistry - A Frisch-grid Ionization Chamber (FGIC) for the measurement of low activity of alpha-particle emitters has been built. The design and performance...     

Three-dimensional supramolecular crystalline materials based on Keggin-based polyoxometalates and 1,2-Bis (4-pyridyl) ethylene for supercapacitor electrodes

Transition Metal Chemistry - To research the application of polyoxometalates (POMs)-based supramolecular crystalline materials in supercapacitors, two new compounds,...     

Correlating conductivity and Seebeck coefficient to doping within crystalline and amorphous domains in poly(3-(methoxyethoxyethoxy)thiophene)

Molecular doping of conjugated polymers (CPs) plays a vital role in optimizing organic electronic and energy applications. For the case of organic thermoelectrics, it is commonly believed that doping CPs with a strong dopant could result in higher conductivity (σ) and thus better power factor (PF). Herein, by investigating thermoelectric performance of a polar side-chain bearing CP, poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET), vapor doped with fluorinated-derivative of tetracyanoquinodimethane FnTCNQ (n = 1, 2, 4), we show that using strong dopants can in fact have detrimental effects on the thermoelectric performance of CPs. Despite possessing higher electron affinity, doping P3MEET with F4TCNQ only results in a σ (27.0 S/cm) comparable to samples doped with other two weaker dopants F2TCNQ and F1TCNQ (26.4 and 20.1 S/cm). Interestingly, F4TCNQ-doped samples display a marked reduction in the Seebeck coefficient (α) compared to F1TCNQ- and F2TCNQ-doped samples from 42 to 13 μV/K, leading to an undesirable suppression of the PF. Structural characterizations coupled with Kang-Snyder modeling of the α–σ relation show that the reduction of α in F4TCNQ-doped P3MEET samples originates from the generation of low mobility carrier within P3MEET's amorphous domain. Our results demonstrate that factors such as dopant distribution and doping efficiency within the crystalline and amorphous domains of CPs should play a crucial role in advancing rational design for organic thermoelectrics.