Polyamine complex, with

The subject matter of this chapter will be subdivided into sections concerning template synthesis of the complexes structural and thermodynamic properties of the complexes with synthetic cyclic polyamines complexes with mixed-donor macrocycles reactivity of the complexes cryptates and complexes with phthalocyanines and porphyrins. 

Aliphatic polyamines, amine adducts and polyamides react with epoxide resins at normal temperatures to give complexes with outstanding chemical resistance. Paints based on this type of reaction must be supplied in two separate containers, one containing the epoxide resin and the other the curing agent , the two being mixed in prescribed proportions immediately before use. 

Other polydentate ligands are polyamines and related ligands. Stability constants of silver(I) complexes with polyamines in dimethyl sulfoxide,419 A-methyl-substituted 4-methyldiethylene-triamines,420 or ethylene- or N- or C-methylated ethylenediamine in aqueous solution have been reported.421 The structure of the silver 1,3-diaminopropane complex, [Ag NH2(CH2)3NH2 ]-C104,422 and complex formation with 1,4-diaminobutane and 1,5-diaminopentane have been reported.423 A dinuclear silver(I) compound with ethylenediamine [(enH)Ag(en)Ag(enH)2]4+ has... 

Silver(I) complexes with polyamines also form molecular aggregates, thus hexamethylenetetramine yields 2D and 3D coordination networks,613 polymeric chains are obtained with diethylene-triamine, tris(2-aminoethyl)amine, or A,A -bis(aminoethyl)propane-l,3-diamine,426 and 2D networks are formed with thiocyanate and bridging polyamines.61... 

Complexation of Cd with a series of polyamine macrocycles, but also related open-chain polyamines, comprising or attached to the 2,2 -bipyridine (bipy) and 1,10-phenanthroline (phen) moieties, has been studied by combined UV/vis spectrometry and potentiometry.24 Formation constants and distribution diagrams of the species present have been evaluated. As a result the thermodynamic stabilities, i.e., the formation constants, are lower for the bipy- and phen-contain-ing ligands than those for Cd complexes with aliphatic oligoaza macrocycles containing the same number of N donors. The probable reason is loss of flexibility of the ligands caused by the size and stiffness of the inserted heteroaromatic moieties. 

It was proposed that mono-protonation of [CuL]2+ to yield [Cu(HL)]2+ occurs initially at the axial nitrogen atom since this Cu-N bond is expected to be weaker as a result of Jahn-Teller distortion. With respect to this, it should be noted that species such as [Cu(HL)]3+ are commonly observed during potentiometric studies of the formation of Cu(n) polyamine complexes. From the proposed mechanism, the following rate law can be deduced ... 

The dissociation rate constant measures directly the value of k 2 in (4.52). The strain resident in multi-ring complexes is clearly demonstrated by some hydrolysis rate studies of nickel(II) complexes. The AFT values for the first bond rupture for Ni(II)-polyamine complexes fall neatly into groups. They are highest for en, containing the most strain-free ring (84 kJ mol ), about 75 kJ mol for complexes with terdentate ligands and only —63 kJ mol for complexes of quadridentate and quinquedentate amines and with NH3 itself. See also Ref. 109. 

Modem work on these and related bare post-transition element clusters began in the 1960s after Corbett and coworkers found ways to obtain crystalline derivatives of these post-transition element clusters by the use of suitable counterions. Thus, crystalline derivatives of the cluster anions had cryptate or polyamine complexed alkali metals as countercations [8]. Similarly, crystalline derivatives of the cluster cations had counteractions, such as AlCLj, derived from metal halide strong Lewis acids [9]. With crystalhne derivatives of these clusters available, their structures could be determined definitively using X-ray diffraction methods. 

---