276866-85-4

Upstream product

• 3731-51-9 2-(Aminomethyl)pyridine 
• 50-00-0 formaldehyd 
• 96-76-4 2,4-di-tert-Butylphenol 
• 194734-57-1 3,5-di-tert-butyl-2-hydroxybenzyl bromide 
• 213775-52-1 N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamine 
• 37942-07-7 3,5-di-tert-butyl-2-hydroxybenzaldehyde 
• 16373-02-7 2,4-di-tert-butyl-6-hydroxymethylphenol 

Downstream Products

• 1451426-90-6 Hf[tBu-ONPyrO]Bn₂ 
• 329009-67-8 Zr[tBu-ONPyrO]Bn₂ 
• 329009-67-8 (C₆H₅CH₂)2Zr(C₅H₄NCH₂N(CH₂C₆H₂(C(CH₃)3)2O)2) 

Relevant academic research and scientific papers

Synthesis, characterization and catalytic reactivity of Mn(III) complexes with a scorpion-like bis(phenolate) ligand: Selective oxidation of primary alcohols to aldehydes

Two new mononuclear complexes of manganese(III), [Mn(bp)(N 3)(CH3OH)]·0.5CH3OH (1) and [Mn(bp)(NCS)0.9(NO3)0.1(CH3OH)] ·CH3OH (2), have been synthesized, where H2

Discrete Ti?O?Ti Complexes: Visible-Light-Activated, Homogeneous Alternative to TiO2 Photosensitisers

A series of novel bimetallic TiIV amine bis(phenolate) complexes was synthesised and fully characterised. X-ray crystallography studies revealed distorted octahedral geometries around the Ti centres with single or double oxo-bridges connecting the two metals. These robust, air- and moisture-stable complexes were employed as photosensitisers generating singlet oxygen following irradiation with visible light (420 nm) LED module in a commercial flow reactor. All five complexes showed high activity in the photo-oxygenation of α-terpinene and achieved complete conversion to ascaridole in four hours at ambient temperature. The excellent selectivity of these photosensitisers towards ascaridole (vs. transformation to p-cymene) was demonstrated with control experiments using a traditional TiO2 catalyst. Further comparative studies employing the free pro-ligands as well as a monometallic analogue highlighted the importance of the ‘TiO2-like’ moiety in the polymetallic catalysts. Computational studies were used to determine the nature of the ligand to metal charge transfer (LMCT) states and singlet–triplet gaps for each complex, the calculated trends in the UV-vis absorption spectra across the series agreed well with the experimental results.

Copper(II) mediated phenol ring nitration by nitrogen dioxide

Cu(ii) complexes of N2O2 type ligands, L1H2 and L2H2 [L1H2 = 6,6′-(((pyridin-2-ylmethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol); L2H2 = 2,4-di-tert-butyl-6-(((3-(tert-butyl)-2-hydroxy-5-methylbenzyl)(pyridin-2-yl-methyl)amino)methyl)phenol], have been synthesized. Addition of nitrogen dioxide (NO2) in THF solutions of the complexes resulted in the nitration at the 4-position of a coordinated equatorial phenolate ring of the ligand frameworks. This nitration did not occur at the phenol ring which is axially coordinated to the metal center. Spectroscopic evidence suggests that the reaction proceeds through a phenoxyl radical complex formation.

Mono- and dinuclear oxidovanadium(v) complexes of an amine-bis(phenolate) ligand with bromo-peroxidase activities: Synthesis, characterization, catalytic, kinetic and computational studies

The mono- and dinuclear oxidovanadium(v) complexes [VVO(L1)(Cl)] (1) and [L1VVO(μ2-O)VO(L1)] (2) of ONNO donor amine-bis(phenolate) ligand (H2L1) were readily synthesized by the reaction between H2L1 and VCl3.(THF)3 or VO(acac)2 in MeOH or MeCN, respectively, and then characterized through mass spectroscopy, 1H-NMR and FTIR techniques. Both the complexes possess distorted octahedral geometry around each V centre. Upon the addition of 1 equivalent or more acid to a MeCN solution of complex 1, it immediately turned into the protonated form, which might be in equilibrium as: [L1ClVVOH]+ ? [L1ClVV-OH]+ (in the case of [L1ClVVOH]+ oxo-O is just protonated, whereas in [L1ClVV-OH]+ it is a hydroxo species), with the shift in λmax from 610 nm to 765 nm. Similar was the case for complex 2. The complexes 1 and 2 could efficiently catalyze the oxidative bromination of salicylaldehyde in the presence of H2O2 to produce 5-bromo salicylaldehyde as the major product with TONs of 405 and 450, respectively, in the mixed solvent system (H2O:MeOH:THF = 4:3:2, v/v). The kinetic analysis of the bromide oxidation reaction indicated a first-order mechanism in the protonated peroxidovanadium complex and a bromide ion and limiting first-order mechanism on [H+]. The evaluated kBr and kH values were 5.78 ± 0.20 and 11.01 ± 0.50 M-1 s-1 for complex 1 and 6.21 ± 0.13 and 20.14 ± 0.72 M-1 s-1 for complex 2, respectively. The kinetic and thermodynamic acidities of the protonated oxido species of complexes 1 and 2 were pKa = 2.55 (2.35) and 2.16 (2.19), respectively, which were far more acidic than those reported by Pecoraro et al. for peroxido-protonation instead of oxido protonation. On the basis of the chemistry observed for these model compounds, a mechanism of halide oxidation and a detailed catalytic cycle are proposed for the vanadium haloperoxidase enzyme and these were substantiated by detailed DFT calculations.

Synthesis and structural characterization of low-valent group 14 metal complexes based on aminobisphenol ligands

Aminobisphenol supported germylenes (1a–3a), stannylenes (1b–3b) and plumbylenes (1c–3c) were synthesized by reaction of Lappert's tetrylenes, [(Me3Si)2N]2M (M?=?Ge, Sn, Pb), with corresponding aminobisphenols R1/sup

Effects of pendant ligand binding affinity on chain transfer for 1-hexene polymerization catalyzed by single-site zirconium amine bis-phenolate complexes

The kinetics of 1-hexene polymerization using a family of five zirconium amine bis-phenolate catalysts, Zr[tBu-ONXO]Bn2 (where X = THF (1), pyridine (2), NMe2 (3), furan (4), and SMe (5)), has been investigated to uncover

Comparison of selected zirconium and hafnium amine bis(phenolate) catalysts for 1-hexene polymerization

The kinetics of 1-hexene polymerization using a family of three zirconium and hafnium amine bis-phenolate catalysts, M[t-Bu-ONXO]Bn2 (where M = Zr (a) or Hf (b), and X = THF (1), pyridine (2), or NMe2 (3)), have been inves

Structure and magnetic behaviour of mono- and bimetallic chromium(III) complexes of amine-bis(phenolate) ligands

Two lithium amine-bis(phenolate) and four chromium(iii) amine-bis(phenolate) complexes have been prepared. The diprotonated tripodal tetradentate ligand precursors 2-tetrahydrofurfuryl-N,N-bis(2-methylene-4- methyl-6-tert-butylphenol), H2[Osub

New dioxo-molybdenum(vi) and -tungsten(vi) complexes with N-capped tripodal N2O2 tetradentate ligands: Synthesis, structures and catalytic activities towards olefin epoxidation

A series of N2O2 tripodal tetradentate ligands derived from di-/tetra-tert-butyl substituted 2-[bis(2-hydroxybenzyl) aminomethyl]X (X = pyridine and benzimidazole) (H2Ln (n = 1-4)) and 8-[bis(3,5-di-tert-butyl-2-hydroxybenzyl)]aminoquinoline (H 2L5) were synthesised through a 4-step reaction scheme involving sequential formylation, reduction, bromination and alkylation. Treatment of H2Ln (n = 1-5) with [WO2Cl 2(dme)] (dme = 1,2-dimethoxyethane) in the presence of triethylamine gave the corresponding cis-dioxotungsten(vi) complexes [WO2(L n)] (n = 1-5). The corresponding molybdenum analogues [MoO 2(Ln)] (n = 1-5) were also prepared from the reaction of [MoO2(acac)2] (acac = acetylacetonate) with H 2Ln (n = 1-3) or [MoO2Cl2(dme)] (dme = 1,2-dimethoxyethane) with H2Ln (n = 4 and 5). All these compounds were fully characterised by a wide range of spectroscopic methods. The molecular structures of [MoO2(Ln)] (n = 2, 4) and [WO2(L2)] were also confirmed by single-crystal X-ray diffraction analysis. The catalytic activities of [MO2(L n)] (M = Mo, W; n = 1-4) towards epoxidation of styrene were also examined.

Accelerated syntheses of amine-bis(phenol) ligands in polyethylene glycol or "on water" under microwave irradiation

Pure amine-bis(phenol) ligands are readily accessible in high yield, often >90%, when the Mannich condensation reactions are performed "on water" or in poly(ethyleneglycol) (PEG). Microwave-assisted synthesis dramatically reduces the time and energy required to prepare these molecules, typically from 24 h to 5 min. The approach seems to be widely applicable (7 amines and 5 phenols were tested to yield a diverse set of bis(phenol) ligands). Significant improvements in yield were observed for ligands derived from di-tert-amyl and di-tert-butyl phenols, possibly resulting from a hydrophobic effect. Single crystal X-ray diffraction data for the ligand derived from p-cresol and N,N-dimethylethylenediamine is reported.