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By Aleksander Abramovich Grinberg

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The brick-red aqueous solutions of this salt give no test for N H 3 or for the free * The SCN~ group is designated here as the thiocyanato group, although in the literature (for example, in Werner's articles) it is often designated as the rhodanato or rhodano group. [The Editors'] COMPOUNDS OF THE HEXA, PENTA, AND TETRAMMINE TYPE 25 cobalt ion, b u t the chlorine is completely precipitated with silver n i t r a t e , even in the cold. I t follows t h a t t h e cobalt ion a n d five molecules of ammonia are bound in a complex ion a n d t h a t all three of t h e chloride ions are in t h e ionic state.

In order to make an intelligent choice of the best conditions for synthesizing a given hexammine, we must have, although it be in general terms, a correlation of the tendency of the given metal to undergo complex formation with the various chemical species that may be present. Certain guides in this respect will be given in connection with the problem of the nature of the forces involved in complex formation (pp. 74 ff). Compounds of the hexammine class are what might be considered the saturated type of complex and they belong to the category which includes ammoniates, aminates, and double salts.

This indicates t h a t four molecules of water in t h e compound [Co(NH 3 ) 5 H 2 0] 2 (C 2 0 4 ) 3 • 4 H 2 0 are n o t co-ordinated b u t are b o u n d in a n o t h e r way, perhaps b y the a t t r a c t i o n of t h e electrostatic fields of t h e complex cation a n d anions. The question of t h e m a n n e r of binding of these excess water mole­ cules is very complicated a n d does not h a v e a single answer. These extra water molecules are often b o u n d less stably t h a n t h e molecules of co-ordinated water.

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