Comprehensive Coordination Chemistry Vol. 3: Main Group and by Geoffrey Wilkinson, Jon A. McCleverty, Robert D. Gillard

By Geoffrey Wilkinson, Jon A. McCleverty, Robert D. Gillard

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12NH3 at -33 “C, which then loses ammonia to give Be40(0Ac)6-nNH3 (n = 3 or 4). These species lose NH3 and give the basic acetate at 180“C. g. 331 An inorganic analogue of these compounds exists in basic beryllium nitrate. This was prepared by heating Be(N03)2 to ca. q4 More complex basic acetates have also been reported. 335 \/ Be o/ o \ \I I / Be Be / \o/ \ (63) Rings containing beryllium, and derived from alkoxides and amides have been r e ~ i e w e d . g. 344These ligands have also seen application as analytical reagents, and the ability of edta to form water-soluble complexes with alkaline earth metal cations is the basis of the determination of hardness in water caused by these two cations.

Acta, 1977, 21, 141. b P . S. Gentile and A. P. Ocampo, Inorg. Chirn. Actu, 1978, 29, 83. 'J . P. Roux ' and J . C. A . Boeyens, Actu Gystullogr. Ser. B, 1970, 26, 526. J. P. Roux and G. J. Krugcr, Acru Urysrallogr.. Sect. E , 1976, 32, 1171. P. S. Gentile, M . P. Dinstcin and J. G. White, Inorg. Chirn. Acto. 1976,19, 67. P. S. Gentile, J . White and S. Haddad, Inorg. Chim. Acta, 1975, 13, 149. Phenacyl kojate (13) was found to form crystalline NaX complexes during its preparation in MeOH. PK with CsBr, CsI, RbI, NaNCS, KNCS, RbNCS and CsNCS, and the complexes MX-2PK with NaCl, KCI, RbCl, CsC1, NaBr, KBr, RbBr, NaI and KI.

Studies have also been made on the selectivity between metals, and on the stability of the complexes. Examples of the effects of loss of terminal group, the introduction of rigid ligand spines and the variation of the terminal group are shown in Figure 7. 5[' Figate 7 Stability constants (log K,) of various podand alkali metal complexes as a function of ionic radius: (a) stepwise loss of terminal groups; (b) ligands with stiffened chains; (c) variation of terminal group (reproduced with permission from reference 33) In the first instance, a relatively small K+/Na+ discrimination is maintained (Figure 7a) but stiffening the spine leads to a movement towards the selectivity of individual cations (Figure 7b).

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