136668-01-4

Upstream product

• 136667-98-6 2-Azido-N-[2-(2-azido-2-methyl-propionylamino)-phenyl]-2-methyl-propionamide 
• 136667-95-3 1,2-bis(2-bromo-2-methylpropanamido)benzene 
• 95-54-5 1,2-diamino-benzene 
• 401846-08-0 N,N’-(1,2-phenylene)bis(2-(1,3-dioxoisoindolin-2-yl)-2-methylpropanamide) 

Downstream Products

• 136668-04-7 5,6-benzo-3,8,11,13-tetraoxo-2,2,9,9-tetramethyl-12,12-diethyl-1,4,7,10-tetraazacyclotridecane 
• 202401-78-3 3,4,8,9-tetrahydro-3,3,6,6,9,-hexamethyl-1H-1,4,8,11-benzotetraazocyclotridecane-2,5,7,10 (6H, 11H) tetrone 
• 1323998-94-2 3,3,6,9,9-pentamethyl-1,4,8,11-tetrahydro-1H-benzo[i][1,4,6,8,11]pentaazacyclotridecine-2,5,7,10(6H,11H)-tetraone 

Relevant academic research and scientific papers

Redox-Active Ligand Assisted Multielectron Catalysis: A Case of CoIII Complex as Water Oxidation Catalyst

Water oxidation is the key step in both natural and artificial photosynthesis to capture solar energy for fuel production. The design of highly efficient and stable molecular catalysts for water oxidation based on nonprecious metals is still a great challenge. In this article, the electrocatalytic oxidation of water by Na[(L4-)CoIII], where L is a substituted tetraamido macrocyclic ligand, was investigated in aqueous solution (pH 7.0). We found that Na[(L4-)CoIII] is a stable and efficient homogeneous catalyst for electrocatalytic water oxidation with 380 mV onset overpotential in 0.1 M phosphate buffer (pH 7.0). Both ligand- and metal-centered redox features are involved in the catalytic cycle. In this cycle, Na[(L4-)CoIII] was first oxidized to [(L2-)CoIIIOH] via a ligand-centered proton-coupled electron transfer process in the presence of water. After further losing an electron and a proton, the resting state, [(L2-)CoIIIOH], was converted to [(L2-)CoIV=O]. Density functional theory (DFT) calculations at the B3LYP-D3(BJ)/6-311++G(2df,2p)//B3LYP/6-31+G(d,p) level of theory confirmed the proposed catalytic cycle. According to both experimental and DFT results, phosphate-assisted water nucleophilic attack to [(L2-)CoIV=O] played a key role in O-O bond formation.

FAR SUPERIOR OXIDATION CATALYSTS BASED ON MACROCYCLIC COMPOUNDS

An especially robust compound and its derivative metal complexes that are approximately one hundred-fold superior in catalytic performance to the previously invented TAML analogs is provided having the formula (I) wherein Y1, Y2, Y3 and Y4 are oxidation resistant groups which are the same or different and which form 5- or 6-membered rings with a metal, M, when bound to D; at least one Y incorporates a group that is significantly more stable towards nucleophilic attack than the organic amides of TAML activators; D is a metal complexing donor atom, preferably N; each X is a position for addition of a labile Lewis acidic substituent such as (i) H, deuterium, (ii) Li, Na, K, alkali metals, (iii) alkaline earth metals, transition metals, rare earth metals, which may be bound to one or more than one D, (iv) or is unoccupied with the resulting negative charge being balanced by a nonbonded counteraction; at least one Y may contain a site that is labile to acid dissociation, providing a mechanism for shortening complex lifetime. The new complexes deliver catalytic performances that promise to revolutionize multiple oxidation technology spaces including water purification.

Synthesis and characterization of Co(iii) amidoamine complexes: Influence of substituents of the ligand on catalytic cyclic carbonate synthesis from epoxide and carbon dioxide

A series of amidoamine ligands (1) and their cobalt(iii) complexes (2) were synthesized and characterized by various spectroscopic techniques including 1H-NMR and X-ray crystallographic techniques. X-ray crystallography shows that one of the complexes, 2a, forms a chiral coordination polymer due to bridge formation with Li+ associated with the complex, although the ligand is achiral. Complex 2 was employed for catalytic synthesis of cyclic carbonates from epoxides and carbon dioxide (CO2) in a solvent free condition. A strong influence of the substituents on the ligand 1 was revealed by the varied activity of complex 2. The presence of electron withdrawing groups such as chloro (2b) and nitro (2c) increases the Lewis acidity of the catalyst, which, in turn, enhances the catalytic activity of 2. An electron withdrawing group containing complexes (2b and 2c) showed exceptionally high catalytic activity with a turnover frequency (TOF) of 662 and 602 h-1 respectively at 130°C and 300 psig CO2 pressure. On the other hand, our studies indicate that a catalyst with an electron releasing group (2d) showed relatively lower activity with a TOF of 488 h-1 under similar reaction conditions. Our results show that cobalt(iii) complexes follow the reactivity order of 2d 2a 2c 2b.

Macrocyclic tetraamido ligands as bleaching catalysts and synthesis thereof

The invention relates to a novel synthetic route for a group of ligands and to an improved catalyst containing the ligand. It provides a method for the synthesis of a ligand having the structure: (I) The invention also provides use of a ligand for inhibiting dye transfer.

Synthesis of a tetraamido macrocycle ligand

An improved synthesis for preparing a tetraamido-macrocyclic ligand, such as 5,6-Benzo-3,8,11,13-tetraoxo-2,2,9,9-tetramethyl-12,12-diethyl-1,4,7,10-tetraazacyclotridecane, H4, in greatly improved yield and in a commercially viable manner, comprising the

A convenient new route to tetradentate and pentadentate macrocyclic tetraamide ligands

(matrix presented) A crucial diamide diamine intermediate in the synthesis of tetradentate macrocyclic tetraamide ligands protected against oxidative decomposition has been synthesized without the use of potentially hazardous organic azide intermediates.

Stable highly oxidizing cobalt complexes of macrocyclic ligands

The first crystallographically characterized neutral square-planar complex of cobalt in an oxidation state higher than 2+, Co(η44-1), is reported. Structural data for this new class of compounds indicate that the macrocycle in Co(η4-1) is Equation Presented X = Cl, Co(η4-1) X = H, Co(η4-2) X = MeO, Co(η4-3) noninnocent; however, EPR data in toluene at 5.9 K (S = 1/2; g1 = 2.558, g2 = 2.170, g3 = 2.017; A2 ≈ 15 G) show that the metal center is the primary reisdence site of the unpaired electron. Co(η4-1) is a stable, yet potent, oxidant which is soluble in benzene and slightly soluble in pentane. The Co(η4-1)/[CoIII(η4-1)]- couple is reversible and found at 0.550 V vs Fc+/Fc in CH2Cl2 (ca. 1.26 V vs NHE). Co(η4-1) slowly oxidized water, yielding H[CoIII(η4-1)], which may also be prepared by the reaction of [CoIII(η4-1)]- with HBF4. Both the redox and the acid/base chemistries of [CoIII(η4-1)]- are reversible. Electrochemical and EPR data are also presented for Co(η4-2) and Co(η4-3).