Inner Complex Chelates. II. Analogs and Polar ... - ACS Publications

Nickel(II) nitrate “6” hydrate (15.2902 g.), which had lost a ... trate-6 hydrate hadbeen of stoichiometric composition, the amount .... Inner Com...
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July 5, 1959

ANALOGS OF BISACETYLACETONEETHSLENEDIAMINE

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solution was colorless. Because the resultant precipitate TABLE 1 contained ammonia which was lost easily, a n attempt was REACTIONSOF XCETYLACETONE WITH SOME COMPLEX IONS made to determine how nearly quantitative this reaction Ion S o h . expected product A n a l . , %J was. Nickel(I1) nitrate “6” hydrate (15.2902 g.), which Basic Cd(CsH;Oz)2 had lost a small portion of its water of crystallization, was Cd(n“8)r + 2 Calcd. Cd, 36.2; C, 38.7; H, 4.34 dissolved in distilled water (100 ml.) and then treated with Found Cd, 33.9; C, 32.65; H, 5.22 concentrated aqueous ammonia (40 ml.). T o the resulting Basic Zn(CaHi0z)Z dark blue solution, acetylacetone (20 ml.) was added slowly Zn(XHa)rfZ Calcd. Zn, 24.8; C, 45.6; H . 5 . 3 5 and a light blue precipitate formed leaving a colorless soluFound Zn, 39.2; C , 41.71; N , 5.70 tion. After drying in a n atmosphere of ammonia, the La(C0a) +3-*‘ Basic La(CsHr0da weight of the precipitate was 15.4481 g. If the nickel niCalcd. La, 31.8 trate-6 hydrate had been of stoichiometric composition, the . ~ quantitative NH~ precipitation amount of N ~ ( C S H ~ O L ) ~for Found La, 39.9 U O S ( C O ~+ ) 2~ - ~ Basic UOz(CsH;02)xn of the nickel would be 15.2996 g. Anal. Calcd. for NiCalcd. U, 48.9 (CjHiO2)2.2NH3: Ni, 20.17; C, 41.27; H , 6.93; N, 9.63. Found U, 43.2 t o 30.8 Found: Ni, 20.03; C, 41.13; H , 6.77; N, 8.64. This Basic Co(C S H I O Z ) ~ compound loses ammonia on standing and is converted Co(NHs)s ’2 Calcd. Co, 29.9; C, 4ti.i; H , 5.48 into the well-characterized green compound, Ni(CjH702)2. Other Reactions.-Attempts to carry out similar reacFound Co, 19.2; C , 38.57; H , ti.93 Ce(Xoa)~-~ Acidic Ce(CsHiOt)ab tions with tungstate, chromite and silicate solutions failed Calcd. Ce, 32.8 completely. The solid reaction products in these cases were Found Ce, 30.8 to 39.8 the hydrous oxides or hydroxides. Reactions in basic conditions were examined with CdA4cetylacetonedissolves in a solution of the urauyl car( N H S ) ~ ’ ~ ,Z ~ I ( N H ~ ) ~La(C03),+3-ZZ, +~, U O Z ( C O ~ ) ~ - ~bonate - ~ ~ complex without causing any precipitation. Only and Co(NH3)ef2. The reaction between Ce(XO3)&-2 and after a considerable amount of acid has been added to this acetylacetone in acidic solution was also investigated. I n solution does a precipitate begin to form. The final preall of these instances the products obtained contained vary- cipitate was obtained from a solution that was still slightly ing amounts of basic materials. The conditions and prodbasic, however. When acetplacetone is added to a soluucts of these reactions are summarized in Table I . tion of ammonium hexanitratocerate(IV),a n initial reaction The precipitate formed with uranium was recrystallized produces the dark blood-red tetrakis-(2,4-pentanediono)from chloroform and analyzed. It was found to contain cerium(1V). The reduction of the cerium(1V) by the ace46.7y0 U and consisted predominantly of bis-(2,4-pentane- tylacetone soon occurs, however, to give a very pale yellow diono)-dioxouranium(V1) and a small amount of impurity. solution. When the p H of this solution is raised by the Since practically the whole of this material was readily slow addition of aqueous ammonia, a light yellow precipitate soluble in chloroform, the separation of the complex from is obtained and it is this latter material to which the table the basic materials could be assured. entries refer. The oxidation products obtained with the Ce(1V) reaction accompanied the complex when i t was recrystallized from material contained 32.9% Ce and the theoretical value for chloroform. Although the material was very dark in color, Ce(CsHiOt)3 is 32.0% Ce. its analysis corresponded closely with that expected for the TEXNESSEE Ce(II1) complex rather than the Ce(1V) complex. This SASHVILLE,

[CDNrRIBUTIOL F R

)M THE

DEPARTMENT O F CHEMISTRY O F CLARK

C>IVERSITY]

Inner Complex Chelates. 11. Analogs and Polar Substituted Analogs of Bisacetylacetoneethylenediimine and its Metal Chelates’s2 BY RICHARD J. HOVES,JOHN J. O’CONNELL AND ARTHURE. ~ I A R T E L L RECEIVED DECEMBER 27, 1958 The syntheses of tetradentate chebting agents of the Schiff base type containing such polar groups as p-bromophenyl, m-nitrophenyl and trifluoromethyl, and the preparation of some of the corresponding metal chelates of Cu( 11), Co( 11), Ni(I1) and V(1V) are described. The tendency of the imino groups in the ligands to be hydrolytically cleaved is decreased by the presence of phenyl or substituted phenyl groups and by chelation of the ligands with metal ions Benzene complexes of bisdibenzoylmethaneoxovanadium( I\’) and of bisbenzoylacetonepropylenediiminooxovanadium( Is’) are described.

The first paper3 in this series described the syntheses and properties of several analogs of bisacetylacetone-ethylenediiinine and their metal chelates. This work has now been extended and includes many derivatives of the parent compound containing highly polar groups such as p-bromophenyl, m-nitrophenyl and trifluoromethyl. In subsequent investigations the dipole moments of these ligands and metal chelates will be studied in the light of the information already available on the simpler urisubstituted Schifl bases and their metal chelates. (1) T h i s work w a s sponsored by the O f f i c e of Ordnance Research under Contract No. DA-19-LAO-ORD-3243 (2) Abstracted in part from a dissertation submitted by Richard J . Hovey to the Faculty of Clark University in partial fulfillment of t h e requirements for t h e degree of Doctor of Philosophy. (3) P. J. hIcCarthy, R . J. HnT~ey,K . Ueno and A . E . .\fartell. T H r s J O U R N A L . 7 7 , 5820 (195.5). ( 4 ) P. J. IIcCnrthp and h E . .\Tartell, i b i d , 78, 2 0 & ,2100 ( l l l 5 b ) .

Results The compounds which have been synthesized are listed in Table I and may be represented by formula I. I n the formula R is the alkyl (or aryl) radical of the diamine and K stands for various polar arid non-polar groups. A s far as it is known none of the metal chelates listed in Table I has been reported H3C

B

\

C=S

/ \

K=C

/cH3

I