Die Tri‐N‐tosyl‐Derivate (VIa) und (VIb) der Titelverbindungen werden jeweils nach zwei Methoden dargestellt: Kondensation des Tri‐N‐tosyl‐diethylentriamins (I) mit den Ditosylaten (IIa) bzw. (IIb) und Kondensation des Bis‐(tosyloxyeth′yl)‐tosylamids (IV) mit den Di‐N‐tosyl‐alkylendi‐ aminen (Va) bzw. (Vb) [im Falle der Kondensation von (IV) mit (Va) entstehen neben (VIa) höhere Kondensationsprodukte in wechselnden Mengen].

Large-scale syntheses of ethylidynetris(methanamine)* (tame), 2,2-bis(aminomethyl)propan-1-ol* (hmmp), 4,4',4?-ethylidynetris(3-azabutan-1-amine)* (sen) and 5,5',5''-ethylidynetris(4-azapentan-1-amine)* (stn) are described. The pure hydrochloride salts of tame, hmmp, sen and stn are isolated directly from the crude amine mixtures by acidification and cation-exchange chromatography. Alternatively, selective complexation as [Co(hexamine)] Cl3 followed by Zn/HCl reduction and cation-exchange chromatography is used to isolate the hexamines sen and stn as their hexahydrochloride salts. These isolation procedures are exceptionally efficient compared with the conventional solvent extraction and (often pyrolytic) high-vacuum distillation methods.

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The new sulfur-bonded compound [Co(tame)( aeaps )] Cl3.H2O has been synthesized by the reaction of aeaps with Co(tame)Cl3 [tame = 1,1,1-tris( aminomethyl )ethane, and aeaps = 2- aminoethyl 3-aminopropyl sulfide or 3-thiahexane-1,6-diamine]. The Co(tame)( aeaps )3+ ion equilibrates in basic solution with the corresponding carbon-bonded species: Co(tame)( aeaps )3++HO-↔ Co(tame)(C-aeaps )2++H2O A salt of the carbon-bonded species, [Co(tame)(C- aeaps )](S2O6), has been isolated and its structure solved by X-ray diffraction analysis ( C- aeaps = 1,6-diamino-3-thiahexan-4-ide). The crystals are orthorhombic, Pna21, with cell dimensions a 20.455(10), b 9.960(10), c 8.982(10) Ǻ at 122(2) K. Preliminary thermodynamic and kinetic data are similar to the recently reported values for the corresponding coordination ion Co( tacn )( aeaps )3+ ( tacn = 1,4,7-triazacyclononane). In basic solution the Co(tame)( aeaps )3+ species exchanges one of its methylene protons orders of magnitude faster than any other methylene protons and also much faster than it forms the alkyl complex as shown by 13C n.m.r. measurements.

Chromatographic separations of a set of closely similar or isomeric cobalt(III) complexes, of the kinds [Co(dien)2]3+, [Co(dien)(medien)]3+ and [Co(medien)2]3+ [dien = diethylenetriamine; medien = 4-methyldiethylenetriamine or 2,2'-methyliminodi(ethylamine)] on SP-Sephadex C-25 and Dowex 50W-X2 cation-exchange resins have been examined with different eluents as sodium salts. The separations obtained appear to be due primarily to differences in the association constants for ion-pairs formed betwen the complex cations and the eluent anions, rather than due to differences in affinities of the free cations for the resins. The strengths of the associations depend on: (1) the availability on the complex cations of appropriately disposed N-H bonds for hydrogen-bonding to oxyanions, and probably on the acidities of these hydrogens (acidity sec-NH > NH2), rather than on polarity of charge distribution, and (2) the basicities of anions, in the order PO43- > SeO32- > (+)-tartrate2- > SO42- > (+)-Sb2(C,4H2O6)22- > Cl- ≈ NO3- > ClO4-. The effects of association with PO43-, SeO32- and (+)-tartrate2- may be so great that complex cations of different charges are not necessarily eluted in the order of their increasing charges. Determinations of charges and polarities (cis/trans) of cationic complexes by chromatographic procedures must therefore be carried out under conditions where association is minimized, as with sodium perchlorate as eluent. Under these conditions, separations are determined largely by cation-resin interactions which are less specific and less discriminating than cation-anion interactions. SP-Sephadex is a particularly sensitive medium for separating different cationic complexes, and tri- sodium orthophosphate and sodium (+)-tartrate are the most effective and generally useful eluents.