Tertiary amine complexes

In sulfamation, also termed A/-sulfonation, compounds of the general stmcture R2NSO2H are formed as well as their corresponding salts, acid hahdes, and esters. The reagents are sulfamic acid (amido—sulfuric acid), SO —pyridine complex, SO —tertiary amine complexes, ahphatic amine—SO. adducts, and chlorine isocyanate—SO complexes (3). 

Table 5 UV-visible spectral data of irawi-dioxo(macrocyclic tertiary amine) complexes of Ru(VI), Ru(V),...

The electrochemistry of both rans-dioxoosmium(VI) and rutheni-um(VI) macrocyclic tertiary amine complexes has been studied in great detail. Both trans-[RuVI(b)2(0)2]2+ and rans-[RuVI(14TMC)(0)2]2 + and its related complexes display similar cyclic voltammograms in aqueous solution (132, 212). At pH < 7, three reversible/quasi-reversible redox couples, corresponding to the redox reactions are observed ... 

Nitrogen Ligands. Amine complexes are not particularly stable but there are cations like [Mn(bipy)3]2+ and tertiary amine complexes, e.g., [MnI3(NMe3)] and [MnI2(NEt3)]2.4... 

Amine complexes are not particularly stable but there are tertiary amine complexes, for example, [Mnl3(NMe3)] and [Mn2(/u-l)2l2(NEt3)2]. The secondary amine can be three-coordinate" as in [Mn N(SiMe3)2 3]. Amides can be also three-coordinate with bridges as in [Mn2(/n-NPr )2(NPr 2)2] and four-coordinate in [Mn(NPh2)4]. ... 

The alcohol-tertiary amine complexation is well established by NMR (2, 17), cryoscopy (10), UV spectroscopy (2) and other techniques (18-20). According to Frisch, 10 to 20% of the amine is complexed by the alcohol (2). 

The evidence for the alcohol-metal complexation is from UV and NMR spectroscopy (2, 5, 17, 21). By cryoscopy, Frisch concluded that the metal is complexed at about 10-20% by the alcohol (10). NMR measurements agree with the formation of a metal-alcohol-tertiary amine complex (17). The proton of the alcohol is indeed shifted by the addition of a tertiary amine (0.22 ppm), an organometallic compound (0.25 ppm) and the combination of these two catalysts (0.72 ppm) respectively. Structure IV could account for the alcohol activation. 

UV and IR spectroscopy as well as cryoscopy have been used to assess the Isocyanate-tertiary amine complexation (3, 6, 22, 27). Di- and trimerization of the isocyanate can take place and complicate the interpretation the occurrence of these side reactions is of course an indirect proof of the isocyanate activation. 

TMED produces a crystalline complex with methyllithium tetramer, but even a large excess of TMED does not break down the tetramer to dimer or monomer (8). This result shows that methyl bridges are stronger than tertiary amine complexation to lithium. 

Coupled transport is not limited to cations. Anions such as Cr2072 can be transported by a completely analogous processes using, for example, tertiary amine complexing agents. 

A typical example of this type of process might be the transport of uranyl ions by tertiary amine complexing agents via the reaction ... 

In addition to p-hydrogen elimination from formally anionic amido and alkoxo groups, p-hydrogen elimination from neutral amine ligands to form iminium products has been observed. This reaction can be part of the pathway for the reduction of metal halides, such as palladium (n) halides, in the presence of tertiary amines. Such a p-hydrogen elimination was observed directly as a reversible process from the tertiary amine complex [Os(NH3) (MeOH)(NH2Pr)] , as shown in Equation 10.16. ... 

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