Anion translocation

A-Aryl sulphonamides have not been investigated in detail, but anion translocation from the S -substituted ring to the A-substituted ring takes place in diaryl sulphonamides 118, ultimately leading to the rearrangement shown in Scheme 51 . ... 

Formation of the most stable organolithium is much faster when a lithium amide is used as the base, since re-deprotonation of the amine by-product provides a mechanism for anion translocation from one site to another. Several examples were discussed in Sections I, II and IV the lithiations of 642 and of 643 with BuLi and with EDA illustrate the point well (Scheme 249). 

Miscellaneous The treatment of allyl 1-bromo-2-naphthyl ether 43 with f-BuLi affords benzyl alcohol 44 via a sequential reaction consisting of bromine-lithium exchange, and anion translocation, followed by a [1,2]-Wittig rearrangement (equation 23). ... 

Figure 2.12 Temperature dependence of AE for MeCN solutions of (i) [Cun(ll)Nin]4 + (open triangles) and (ii) an equimolar mixture of [Cun(12)]2+ and [NiH(13)]2+ (filled triangles), in the presence of 0.5 equivalent of CP. AE is the peak separation in the DPV profiles in Fig. 2.10 and refers to the neat anion translocation equilibria (2.3) and (2.4). The slope of the AE versus temperature straight line gives AS° for pertinent equilibrium.

Fabbrizzi, L., Gatti, F., Pallavicini, P., Zambarbieri, E., Redox-driven intramolecular anion translocation between transition metal centres. Chem. Eur. J. 1999, 5, 682-690. 

Barluenga, J. Fananas, F. J. Sanz, R. Marcos, C. Trabada, M. On the reactivity of o-lithioaryl ethers tandem anion translocation and Wittig rearrangement. Org. Lett. 2002, 4, 1587-1590. 

Hence, citrate formation, anion translocation (The other way, goes malate, say)... 

Translocation systems of the inner mitochondrial membrane are listed in Table 14-5. Anion translocators are responsible for electroneutral movement of dicarboxylates, tricarboxylates, a-ketoglutarate, glutamate, pyruvate, and inorganic phosphate. Specific electrogenic translocator systems exchange ATP for ADP, and glutamate for aspartate, across the membrane. The metabolic function of the translocators is to provide appropriate substrates (e.g., pyruvate and fatty acids) for mitochondrial oxidation that is coupled to ATP synthesis from ADP and Pj. 

Redox-Driven Anion Translocation Between Metal Centers. 108... 

Thus, the two tetramine receptors cyclam and tren were linked by a 1, 4-xylyl spacer to give system 14, tren-cyclam. The heterodimetallic complex [Cu(II)(tren)-Ni(II)(cyclam]4+ operates chloride anion translocation between copper and nickel centers, through the Ni(II)/Ni(III) couple, in an MeCN solution [36]. In particular, when 1 equivalent of CP is added to an MeCN solution of the heterodimetallic complex [with the nickel center in the Ni(II) state], the anion goes on the Cu(II) ion. In particular, since the log K value for the 1 1 adduct formation equilibrium is 5.7, in a lO-3 M solution of the heterodimetallic complex, 95% of the CP ion is bound to Cu(II), while the remaining 5% is dispersed in the solution. The solution has a blue-green color, due to an absorption band centered at 460 nm, pertinent to the [Cu(II)(tren]2+ fragment of the heterodimetallic complex [Cl-to-Cu(II) CT transition). If in an... 

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