Primary amines chelation

Bauer, D.J., R.E. Lindstrom and K.B. Higbie, 1968, Extraction Behavior of Cerium Group Lanthanides in a Primary Amine-Chelating Agent System, RI 7100 (US Bureau of Mines) 12 pp. 

Ligands with S donors in addition to N and or O donors bound to Co11 are reasonably large in number. For example, the 4-amino-3-alkyl-l,2,4-triazole-5-thione can bind Co11 as a chelate employing the primary amine and thione substituents on the five-membered ring,510 whereas the trifluoromethyl ligand (afmt) forms [Co(afmt)2(H20)2](N03)2, defined as the A -irons isomer... 

The reaction of 2,2 -dithiodibenzaldehyde with Ni11 complexes containing coordinated primary amines results in Schiff base condensation and cleavage of the disulfide bond to form a chelating... 

Singh et al. (2006) also used cycloaddition to prepare carbon nanotubes containing indium labeled diethylenetriamine pentaacetic acid (DTPA) derivatives (Figure 15.17). In the initial modification, a SWNT was derivatized to contain a primary amine at the end of a short PEG spacer. The resultant water-soluble nanotube then was reacted with DTPA to create a metal chelating group at the end of the chain. Subsequent loading of the chelate with mIn created a radionuclide-SWNT complex for in vivo biodistribution studies. 

Ihnat and coworkers substituted the primary amine group with a series of gradually increasing alkyl amides 113-119, aromatic amides 120 and 121, succinamide 122 and methylsulfonamide 123 with a systematic increase in partition coefficient (octanoFwater), to increase permeability while retaining iron-chelating ability. The formamide derivative... 

In our NMR studies 143,147,148,322-324) of amine and other adducts of Ni[R-dtp]2 complexes neat amines were employed in order to eliminate variations in extent of association (H-bonding) of the amines, to permit observation of NH proton shifts, and to maximize the concentration of the preferred adduct. The use of high concentration of primary amines in solutions with Ni[R-dtp]2 complexes can lead to products other than those expected, e.g., with aliphatic diamines, the R-dtp anion salts of f/zs(diamine)nickel(ll) chelates are obtained ). Furlani and co-workers ) have shown that Ni-(ethyl-dtp)2 reacts with n-butyl amine to yield complexes containing the NiS2N4 chromophore, presumably with monodentate ethyl-dtp. In all work with adducts it is necessary to assure that the complexes, adduct molecules and solvent systems are anhydrous. A number of authors 132,284,295,329) shown that Ni[ R-dtp ]2 complexes decompose when in contact with water. 

A statistical calculation was carried out and the calculated value of x at saturation (0.63) was nearly equal to the experimental value of x2 The profile for the BPEI-Co(III) complex was considered to be as in Fig. 2(b), with the Co(III) chelates coordinated preferentially to the end primary amine groups of the branched poly(ethyleneimme)4. ... 

The most important reaction of this type is the formation of imine bonds and Schiff bases. For example, salicylaldehyde and a variety of primary amines undergo reaction to yield the related imines, which can be used as ligands in the formation of metal complexes. However, it is often more desirable to prepare such metal complexes directly by reaction of the amine and the aldehyde in the presence of the metal ion, rather than preform the imine.113 As shown in Scheme 31, imine formation is a reversible process and isolation of the metal complex results from its stability, which in turn controls the equilibrium. It is possible, and quite likely, that prior coordination of the salicylaldehyde to the metal ion results in activation of the carbonyl carbon to amine nucleophilic attack. But it would be impossible for a precoordinated amine to act as a nucleophile and consequently no kinetic template effect could be involved. Numerous macrocyclic chelate systems have been prepared by means of imine bond formation (see Section 61.1.2.1). In mechanistic terms, the whole multistep process could occur without any geometrical influence on the part of the metal ion, which could merely act to stabilize the macrocycle in complex formation. On the other hand,... 

It has been well established that metal-directed condensation between metal-coordinated primary amines with aldehydes and dibasic acids such as nitroalkanes or primary amines provide a ready route to selected pendant arm maciocyclic ligands and their metal complexes [20], In such a reaction a new six-membered chelate ring is... 

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