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101.
Anatoli I. Brusilovets V. Bdjhola T. Lis A. Savitsky 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):729-732
The interaction of 1,3,2,4 -oxaazaphosphatitanetidines with chlorides of aluminium and zirconium, alcohols, piperidine and R2NBr (R=SiMe3) has been studied. The reaction routes have been determined with NMR spectra and X-ray structure analyses. 相似文献
102.
Titanium tetrachloride in ethyl acetate can be reduced by Mg powder to the corresponding low‐valent titanium complexes, which can reduce some aromatic aldehydes and ketones to the corresponding pinacols in 38–85% yields within 15–60 min at rt with stirring. 相似文献
103.
A Supramolecular Chiral Auxiliary Approach: “Remote Control” of Stereochemistry at a Hierarchically Assembled Dimeric Helicate
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David Van Craen Prof. Dr. Markus Albrecht Prof. Dr. Gerhard Raabe Fangfang Pan Prof. Dr. Kari Rissanen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3255-3258
Dimeric hierarchically‐assembled titanium(IV) helicates are in solvent‐dependent equilibrium with the corresponding monomers. Statistically formed mixtures of such complexes bearing chiral stereocontrolling ligands and achiral diene‐substituted ligands show high diastereoselectivity and reasonable enantioselectivity in the Diels–Alder reaction with maleimides if the reaction proceeds with the dimer but not with the monomer. Thus, solvent dependent switching between the monomer and dimer enables on/off switching of the enantioselectivity. 相似文献
104.
Dr. Quentin Bonnin Tereza Edlová Dr. E. Daiann Sosa Carrizo Prof. Dr. Paul Fleurat-Lessard Dr. Stéphane Brandès Dr. Hélène Cattey Dr. Philippe Richard Prof. Dr. Pierre Le Gendre Dr. Adrien T. Normand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18175-18187
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). 相似文献
105.
Ping Yin Yucai Hu Chunhua Wang Yuan Tian Qinghua Tang Chongrong Bao 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):514-522
Theoretical studies on the thermodynamic and kinetic properties of the reactions of Ti+ with sulfur transfer reagent SCO via the C═S bond activation pathway have been carried on using DFT/B3LYP method, general statistical thermodynamics, and Eyring transition state theory with Wigner correction. The relevant reactions include reaction 1 4 Ti++1SCO → 4 IM 1 → 4 TS 1 → 4 IM 2 → 4 TiS++ 1 CO, and reaction 2 4Ti++1SCO →4IM1→ CP →2IM2→2TiS++1CO in which the spin multiplicity changes from the quartet state to the doublet state in the crossing region. It is concluded that the increase of the temperature is favored to the reaction 1 process, since the equilibrium constants (K) rises from 0.566 × 10[P]-9 at 200 K to 0.109 × 100 at 1200 K, and the reaction rate constant (k) from 0.222 × 100 s[P]-1 at 200 K to 0.540 × 10 11 s[P]-1 at 1200 K. Moreover, reaction 1 is endothermic, and non-spontaneous in the way the entropy increases, while reaction 2 is exothermic and spontaneous in the way their entropy decreases. The reaction path 2 is the energetically favorable channel, and its thermodynamic data change not largely with the rise of temperature. 相似文献
106.
107.
介绍了钛材碱洗脱脂除油和酸洗除去氧化皮的原理和方法,重点阐述了钛材碱洗除油和酸洗除去氧化皮的工艺条件、工艺流程和设备. 相似文献
108.
通过在300℃下焙烧2h制备了磷酸钛固载15%磷钨酸H3PW12O40(简记为HPW)非均相酯化催化剂HPW/Ti3(PO4)4;采用红外光谱仪分析了催化剂的结构;基于异戊酸与正己醇的酯化反应考察了催化剂用量、n(正己醇)∶n(异戊酸)、反应时间、带水剂种类和催化剂重复使用性能等因素对酯化率的影响.结果表明,该催化剂催化合成异戊酸己酯的适宜反应条件为:0.2mol异戊酸,催化剂用量0.6g,n(正己醇)∶n(异戊酸)=1.6∶1,反应时间4.5h,环己烷10mL;相应的酯化率达95.1%.与此同时,该催化剂循环利用6次后酯化率不低于84%. 相似文献
109.
110.
A novel protocol for intramolecular ketyl-olefin radical cyclization with low-valent titanium reagent is outlined. It allows the formation of the benzopyran nucleus from ortho-allyloxy propiophenones as the sole product in moderate yields via intramolecular radical cyclization. 相似文献