Alkali Metal Complexes with Organic Ligands by J. D. Dunitz PDF

By J. D. Dunitz

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54 . Mg2+ . 0 . 80 . 9 . 78 . 9 . 10 Ba2+ . 16 -- Ag+ . 74 -- T1+ T a b l e 7. 75 pb2+ (3) (104) (3) (65) (3) Ref. O ~0 0~ o~ o~ 0. O o~ 9 o 8. 1 3 . 3 . K+ . 5 b) -- -- -- -- . Rb + . . . 6 e) 2 . 8 ct) . Cs + . . 6 b) -- 3 . 2 b) -- -- -- -- Sr2+ . . 3 b) -- 3 . 6 ( i n W ) -- Ag+ (65) (65) (135) (65) (65) (65) (65) (65) (65) {65) (65) (65) (65) (65) Ref. Stability Constant (log Ks) o/alkali and alkaline-earth metal cation complexes with ligands o] type D ( K s in lmo1-1 at 25 ~ 6 Compound Table M 26 : M 25 b) e) a) e) a) -- M 24 .

Both ligands have about the same cavity radius but 88 contains two oxygen sites less than 30. e. each oxygen site removed amounts to a factor of about 102. The nature of the sites has also a clear influence on complex stability. All ligands listed are electrically neutral. They contain ether, amine or thioether binding sites which contribute to the stability of the AC complexes following the sequence of electrostatic interactions 0 > N > S (Table 3). Acetal oxygens are less effective than ethylene-dioxy groups (107).

Synthetic hgands are of special interest since, in principle, stepwise variations in the different parameters may be brought about via structural modification of the carrier. An efficient and selective carrier should have the following features (see also I6, 134) : 1. 2. 3. 4. form stable and selective complexes; show fast exchange kinetics; have a lipophilic outer surface so as to be soluble in organic media; be of not too large size so as to diffuse rapidly. The transport selectivity is determined both by the selectivity of the complexation itself and by the exchange kinetics.

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Alkali Metal Complexes with Organic Ligands by J. D. Dunitz


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