July, 1934
NOTES
1551
that there is a limited amount of water available for reactioh. No blue color is obtained by rubbing sodium or potassium on ice. Calcium shows no colorations during its dissolution in water. Potassium gives infrequent and very small colored regions during its reaction with methyl (8) Von Wartenberg and Schultze, Z.phrsik. Chem.. BP, 1 (1929). alcohol but gives none with ethyl alcohol. LithMINNEAPOLIS, MINN. RECEIVED MAY7, 1934 ium and sodium give no such coloration with methyl alcohol. While these observations are not entirely conBlue Colored Water Solutions of the Alkali clusive it is felt that they do indicate that the Metals alkali metals form unstable blue colored solutions BY HENRYJ. WOLTHORN AND w. CONARD FERNELIUS in water. The realization that metals are physiNumerous investigators have observed that the cally soluble in water greatly conditions the point alkali and alkaline-earth metals dissolve in liquid of view which one is to adopt toward such procammonia, the alkyl. amines' and the fused alkali esses as reduction by sodium amalgam and soluamides2 to give solutions of an intense blue color. tion of metals in acids6 (5) See for example J. N. Bransted, THISJOURNAL, 63, 3626 fn. Kraus has clearly demonstrated that the solutions (1931). in ammonia contain the ordinary metal cations THEOHIOSTATE UNIVERSITY and ammoniated electrons. Franklins has long COLUMBUS, RECEIVED MAY10, 1934 OHIO thought that the alkali metals would also give similarly colored solutions in water were it not for the fact that the metals react extremely rapidly A Note on the Stereochemistry of Four Covalent with this solvent. A few years ago it was demon- Palladium, Platinum and Nickel Compounds BY F. P. DWYERAND D. P. MELLOR strated that sodium dissolves in molten sodium hydroxide (a derivative of water) to give a blue The resolution of four covalent palladium,' solution.2 More recently evidence has been ob- platinum12and nickel3 compounds into optically tained in this Laboratojr which indicates that the active antipodes, and the separation of cis-trans alkali metals are capable of forming very unstable isomers of the type [Pt XZY~], where X = "8, blue solutions in water. A brief rCsum6 of this (&H&S, and Y = C1, Br, . ., lead to the concluevidence follows. sion that either (a) planar and tetrahedral conBy confining potassium in a short length of 6 figurations of the bonds about the central metal mm. glass tubing4 so that the metal is held a t the atoms are possible in different complexes, or (b) bottom of a beaker of water and the reaction takes that the disposition of the bonds is in all cases a place in a confined space, there appear near the pyramidal one, a configuration which would acmetal at irregular intervals transient blue colored count for both types of isomerism. To establish patches of about the same intensity of color as convincing experimental evidence for (b) it must that of the alkali metals in other solvents. When be shown that a given four covalent complex conlithium is firmly packed into a piece of glass tubing taining two unsymmetrical chelate groups can exof small diameter and brought into contact with ist in cis and trans forms, the latter only of which water, a blue line a t the reacting interface is is resolvable into optical antipodes. While no frequently visible. Although sodium similarly completely satisfactory evidence along these lines confined shows no blue coloration, some such is yet available, the indications are sufficient to coloration is noticed when bits of the metal adhere warrant further search. For example, Drew and to the side of a beaker above the water level so Head4 have separated cis-trans isomers of bisiso-
ethylene and a hydrogen atom. However, this assumption does not appear to be in agreement with results of Bates and Taylorlb on the mercurysensitized reaction in the presence of hydrogen, or the results of von Waxtenberg and Schultze with Wood's hydrogenes
.
(1) For bibliography and review see C. A. Kraus, J . Franklin Insl., 212, 537--62 (1931); W. C. Johnson and W. C. Fernelius, J . Chem. Ed., 6, 20-35 (1929); W. C. Johnson and A. W. Meyer. Chem. Reuvicws, 8, 278-301 (1931). (2) For bibliography see W. C. Fernelius and F. W. Bergstrom, J . Phys. Cham., 36, 746 fn. (1931). (3) E, C. Franklin, private communication. (4) For method of filling these tubes see G. S . Bohart, J . Phys. Chem., 19, 539 fn. (1915); W. C. Fernelius and I . Schurman, J . Chem. Ed., 8, 1'765-6(19291.
butylenediamine platinous chloride; on the other hand, Reihlen and Huhn2 have obtained incomplete evidence of optical activity in the cation of (1) Rosenheim and Gerb, Z.anorg. Chem., 210, 289 (1933). (2) Reihlen and Hdhn, Ann., 489, 42 (1931). (3) Reihlen and Hiihn, i b i d . , 499, 144 (1932). (4) Drew and Head, J . Chem. SOL., 221 (1934); Nature, 132, 210 (1933).
