Cobalt triamines

The medium-ring cyclic triamines, 1,4,7-triazacyclononane (tacn), 1,4,7-triazacyclodecane (tacd), 1,4,8-triazacycloundecane (tacud), and 1,5,9-triaza-cyclododecane (tacdd) have been synthesized and the cobalt complexes [Co(tacn)2]Br3, [Co(tacd)2]Br3,H20 and [Co(tacud)BrCl2] isolated. It has been suggested that the structures are of the sandwich type [viz. (95) and (96) "] and, for this reason, the reporter looks forward to publication of X-ray structural analyses. 

A GENERAL NON AQUEOUS PREPARATION OF COBALT(III) AND NICKEL(II) DIAMINE AND TRIAMINE COMPLEXES... 

Co(H2NCH2CH2NHCH 2CH2NH2)2](NO 3)3 is named as Bis (diethylene triamine) cobalt(III) nitrate. 

We found that when an aqueous solution of chloropentammino-cobalt(III) dichloride, [(NH3)5ClCo]Cl2, was boiled with two equivalents of the triamine, the cold concentrated solution deposited the orange crystals of bis(triaminopropane)cobaltic trichloride (VII X = Cl), which when treated in aqueous solution with sodium iodide deposited the orange-brown tri-iodide (VII X = I) (29)j and with sodium thiocyanate deposited the pale brown trithiocyanate (VII X = SCN) (28), The almost colorless crystals of bis(triaminopropane)rhodium(III) tri-iodide (VIII X = I) were similarly prepared (1925) (29). 

A bis-triamine [Co(tame)]3+ complex also reacted with formaldehyde and aldehydes of carboxylic acids RCHO (where R is CHs, C2H5, or (CH3)2CH)) to form cobalt (III) triiminosarcophaginates... 

The E values for macrobicyclic cobalt complexes in aqueous solutions differ by 1400 V (from -550 to 840 mV). For nonmacrocyclic cobalt complexes with diamines and triamines, the E values change from -630 to 280 mV. The potentials for [Co(NH3)6] and [Co(en)3] ions occupy an intermediate position in this range [4, 344]. 

A recent paper by Cooper et al. [155] reported a fairly strong catalytic effect of an unidentified zinc compound on the reaction of an aromatic isocyanate with 3,3 -dichlorobenzidine. Axelrood et al. [184] found diethylene triamine and stannous octoate to be powerful cateilysts for the reaction of phenyl isocyanate and an aromatic diamine, whereas di-butyltin dilaurate and cobalt naphthenate had only a mild effect in their system. 

DIETHYLENE TRIAMINE or DIETHYLENETRIAMINE (111-40-0) Combustible liquid (flash point 208°F/98°C oc). An organic base. Ignites spontaneously with cellulose nitrate, and possibly with other nitrogen compounds. Silver, cobalt, or chromium compounds may cause explosions. Contact with nitromethane forms a heat-, friction-, and shock-sensitive explosive. Incompatible with acids, acrylates, aldehydes, alcohols, alkylene oxides, caprolactam solution, cresols, organic anhydrides, substituted allyls, epichlorohydrin, glycols, halo-genated compounds, isocyanates, ketones, mercury, phenols, strong oxidizers, vinyl acetate. Attacks aluminum, copper, cobalt, lead, tin, zinc, and their alloys. 

Co(dien)(SCN)20H] Dithio-cyanatohydroxo (diethylene-triamine)cobalt(III), 7 208... 

The mechanism of the reaction of (ethylenediamine)(diethylene-triamine)cobalt(II) complexes with O2 to give the mononuclear Co(III) compound has been investigated by using Co It is concluded that the peroxo... 

Azide ion, both free and bound to metal-ion complexes, also absorbs strongly in this range. A comparison between the infrared spectra of azide bound to diethylene-triamine Zn(II) and Co(II) complexes or to the cobalt-enzyme and the corresponding spectrum for the native enzyme showed that the azide ion is coordinate to the Zn(II) atom of the native enzyme. Examination of the difference spectra in the presence of both azide and CO2 showed that the bound azide sterically interferes with the binding of CO2 in the hydrophobic cavity adjacent to the Zn(ll). 

Cinnamoyl chloride Cobalt carbonate hydroxide N-Coco dipropylene triamine Cocopropylenediamine C9-11 pareth-3 C9-11 pareth-6 C9-11 pareth-8 C10-12 pareth-5 C12-15 pareth-6 Cresylic acid 2-Cyanoethyltriethoxysilane 3-Cyanopropyltrichlorosilane Cyclohexane Cyclohexene oxide Cyclopentadiene Decamethylcyclopentasiloxane Decane nitrile 1-Decanethiol Decanoyl chloride Dehydroacetic acid... 

Nicotinic acid (X-17) can be obtained by an interesting electrolytic trimerisation of acrylonitrile to 1,3,6-tricyanohexane (X-15). The latter is reduced with Raney Cobalt to the corresponding triamine, which, in turn, is catalytically cychzed to 3-(cj-amino-n-butyl)piperidine (X-16, R = H). The acetylated piperidine (X-16, R = OAc) is dehydrogenated and oxidized to the vitamin (X-17). ... 

In the case of aliphatic triamines, (1-1-1) template condensation can be achieved if the number of atoms separating terminal NH2 groups equals 7. Thus, by interaction of dipropylenetriamine with dap on manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) matrices, it is possible to synthesise the 14-membered macrocyclic ligand L695 as appropriate complexes (Eq. 3.30) [71, 72, 74-76]. 

When dap reacts with an aromatic 3,3-triamine in the presence of nickel(II), copper(II) or cobalt(II) perchlorate in ethanol, macrocyclic complexes with tetra-dentate ligands [M(L712)](C104)2 and having octahedral structures are isolated (Eq. 3.35) [73]. 

Phthalic anhydride Polyadipic acid anhydride Coal tar pilch and diethylene triamine Tall oil plus cobalt naphthenate Organosiloxanes containing Si-OH groups, plus catalysts [ferric naphthenate, ferric bromide, zinc acetate, zinc benzoate, zinc stearate]... 

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