Amines metalation

Maleic anhydride Alkali metals, amines, KOH, NaOH, pyridine... 

Macrocyclic coordination compounds formed bv condensation of metal amine complexes with aliphatic carbonyl compounds. N. F. Curtis, Coord. Chem. Rev., 1968, 3, 3-47 (78). 

First reported by Fredenhagen in 1926 F3, F4), the graphite-alkali-metal compounds possess a relative simplicity with respect to other intercalation compounds. To the physicist, their uncomplicated structure and well defined stoichiometry permit reasonable band-structure calculations to be made S2,12) to the chemist, their identity as solid, "infinite radical-anions frequently allows their useful chemical substitution for such homogeneous, molecular-basis reductants as alkali metal-amines and aromatic radical anions N2, B5). 

A number of synthetic procedures are available (Ai2). (2) For precisely defined stoichiometries, the isobaric, two-bulb method of Herold is preferred H5, H6, H2). (2) To generate compounds suitable for organic synthesis work, graphite and alkali metal may be directly combined, and heated under inert gas (Pl, lA). (5) Electrolysis of fused melts has been reported to be effective iN2). 4) Although alkali metal -amine solutions will react with graphite, solvent molecules co-inter-calate with the alkali metal. Utilization of alkali metal-aromatic radical anion solutions suffers the same problem. 

The bacterial resistance of silk fibroin can be improved by treatment at low pH values in aqueous solutions of metal ions and at high pH values in solutions of metal-amine complexes, using untreated silk or silk pretreated with an aqueous solution of tannic acid (10.183). Suitable metals include Cu, Zn, Ni, Fe and Ag [533]. It is to be expected that treatment with such metal compounds will be subject to restrictions in environmentally sensitive areas. 

Maleic anhydride Manganese dioxide Alkali metals, amines, KOH, NaOH, pyridine Aluminum, hydrogen sulfide, oxidants, potassium azide, hydrogen peroxide, peroxosulfuric acid, sodium peroxide... 

Bjeirum, J. Metal Amine Formation in Aqueous Solution, P. Haase and Son, Copenhagen (1941). 

The procedure has several advantages iron will remain in the leach residue nickel and cadmium are almost completely leached and form metal-amine complexes in solution and, finally, the buffer capacity of the solution... 

Electrical Transport Properties of Metal-Ammonia and Metal-Amine Solutions... 

The deviations of experimental slopes for dilute solutions of metal-ammonia and metal-amine conductance plots from the limiting Onsager slope can be used conveniently to calculate association constants for the postulated, nonconducting species responsible for the deviations. Precise association constants of sufficient magnitude may be taken somewhat as confirming the probable existence of the postulated complexes. 

The common facts that obviously permeate all aspects of the transport properties of metal-ammonia and metal-amine systems are ... 

Phenomenologically, in dilute solutions the metal-ammonia and metal-amine solutions have transport properties quite similar to electrolytes in similar solvents, and consequently the types of interactions involved are probably similar. 

It is clear that the study of solvated electron reaction rates, using metal-amine solutions as the source of electrons, is currently in the early stages of development, and the conclusions drawn must be very limited in scope. If the species present in metal solutions in ethylenediamine and other amines can be firmly identified, the techniques described in this paper should prove useful for studying reactions of solvated electrons with... 

Table 5-1. The pKa values of some metal-amine complexes.

Aromatic primary diamines, dithiols, and diethynyl compounds are oxidatively polymerized with metal-amine complexes as the catalyst to yield poly (azopheny-lene) [78], poly(disulfide) [79], and polydiyne [80], respectively (Figure 7, Eq. 

Sulfonamides also can be metalated at the nitrogen-bound carbon [247] (Scheme 5.27). The sulfonyl group is, however, usually not well suited for the stabilization of a-metalated amines because sulfinate is a good leaving group, and imines... 

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