METAL ION COMPLEXES OF AROMATIC AMINO ACIDS II 527

M etal Ion Com plexes of A rom atic A m ino Acids

II. N-Substituted Amino Benzoic Acids

J. S m it h D ec k e r a n d H e r sc h e l F r y e
University of the Pacific, Stockton, California

(Z. N aturforschg. 21 b, 527— 529 [1966] ; eingegangen am 22. F ebruar 1966)

This study has indicated that substitution on the nitrogen atom in aminobenzoic acid markedly
decreases complex forming ability; this is especially true in the case of bulky electrophilic groups
such as phenyl and acetyl. In these cases, the usual evidence accepted for the formation of coordi­
nation complexes was not present, and it was therefore concluded that only salts were formed from
ligands bearing these groups on the nitrogen atom. The presence of the methyl group on the amino
nitrogen reduces the ability to form complexes and also reduces the stability of the few complexes
formed; this is in contrast to the substitution of methyl and other small groups on the ring.
Using carbon-hydrogen ratios and infrared data, the structures assigned to the complexes are
square planar with the exception of tetrahedral zinc (II) complexes. Usually water was present in
the complex which stubbornly resisted removal; at least some of this water may have been co­
ordinated, particularly in the cases where cations are known to prefer octahedral symmetry. The
ratios for the complexes prepared from A-methylanthranilic acid were in every case two ligand
anions to one metal cation. Ultraviolet-visible data were obtained with difficulty and in general
substantiated the evidence obtained by infrared analysis. The presence of water tended to obscure
these results, and the very limited solubility of the complexes in water and in other appropriate
solvents precluded intensive analysis via ultraviolet-visible absorption spectrophotometry.
Five coordination complexes and twenty-eight salts were produced of the forty-four combinations
possible with these four acids as ligand source. The five complexes studied were previously un­
reported; however, the copper (II) and cadmium (II) complexes of iV-methyl- and of iV-phenyl-
arthranilic acid reported by other workers 2 were, on the basis of the criteria used in this study,
salts rather than coordination complexes.
The stability series as determined from the degree of shifting in the infrared regions around
3400 cm -1 and 1000 cm- 1 were shown to differ markedly from those series obtained for ring
substituted aminobenzoic acids.

In a previous p ap e r of this series 1 the effects of
rin g substitution on the ability of an th ra n ilic acid
to fo rm stable chelates w ith various m etal ions were
described. In the present p ap er, data will be p re ­
sented to illustrate the effect of substitution of v a ri­
ous groups on the am ino n itrogen of a n um ber of
arom atic am ino acids. The copper (II) and cad ­
m ium (II) com plexes of A -m ethyl and A -phenyl
an th ran ilic acids have been s tu d ie d 2, and th e ir
stability constants have been m easured. T he present
rep o rt describes research into the synthesis of m etal
ion com pounds w ith fo u r A -substituted acids:
A -m ethylanthranilic, A -phenylanthranilic, N ,N -di-
p h enylanthranilic, and A -acetylanthranilic. C ations
used w ere m agnesium ( I I ) , calcium ( I I ) , chrom i­
um ( I I I ) , m anganese ( I I ) , iro n ( I I ) , iro n ( I I I ) , co­
b alt ( I I ) , n ic k e l(II), c o p p e r (I I) , z in c ( I I ) , and ca d ­
m ium ( I I ) . R eaction p roducts w hen form ed w ere
subjected to in fra red abso rp tio n spectrophotom etry
to determ ine w hether coord in atio n com plexes or
salts h ad been fo rm ed ; these data w ere also used to
p red ict the relative o rd er of stability of the chelates
form ed. In addition, elem ental analyses fo r carbon
an d hydrogen were m ade and som e ultraviolet-
visible spectra were taken. O ther d ata such as solu­
bilities in a variety of liquids, relative m o lar con­
ductances, and p er cent yield of p ro d u ct are also
p resented w here they w ere determ ined.
The m ethods used in synthesizing the com pounds
studied have been described previously and need not
be re p e a te d 1. In general, sm aller am ounts of the
p u re acid were available for recrystallization and
conversion to the sodium salt th an was the case w ith
the acids of the rin g substituted series; yields are
therefore less th an those presently rep o rted , and the
sm aller am ounts m ade q u antitative m easurem ent
im possible. Of the forty-four possible com binations
of m etal cation and lig an d anion, th irty -th ree yielded
precipitates which were am enable to the various
analytical techniques; of these, only five produced
definite shifts in selected regions of the in fra red
ab sorption spectrum in d icatin g co o rd in atio n com-

1 J. D ecker and H. F rye, Z. Naturforschg. 2 1 b , 522 [1966]. 2W. H a rr is a n d T. S w e e t, J. chem. Physics 60, 509 [1956].

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528 J. SMITH DECKER AND H. FRYE

plex form ation. All five of the complexes studied The m easurem ent of m o lar conductances proved
w ere produced by ./V-methylanthranilate ion. In m ost im possible in w ater because of solvation effects.
cases, w ith both com plexes and salts, precipitation M easurem ents w ere m ade in absolute ethanol fo r the
was im m ediate; how ever the salts produced with c o b a lt(II) an d c o p p e r(II) salts of A^-acetylanthran-
yV-acetylanthranilate often req u ired over an h o u r of ilic acid, an d fo r app ro x im ately 8 X 1 0 -5 m olar so­
stan d in g at room tem perature to produce solid. In lutions, these w ere 7.7 x 1 0 ~ 2 m hos and 3.5 x 1 0 -2
the case of 7V,./V-diphenyJanthranilate, iron ( I I ) , m hos respectively.
iro n ( I I I ) , chrom ium ( I I I ) , and m anganese (II) S tudy of the in fra red spectra of the solids in d i­
caused the free acid to precipitate. cated th at only the com pounds obtained w ith /V-methyl-
C olors of the various precipitates w ere quite an th ran ilic acid prod u ced com plexes, and therefore
v ariab le and n ot alw ays characteristic of the m etal no elem ental analyses w ere done on com pounds from
cation used. T able I presents a list of these colors the other ligands. C adm ium ( I I ) , c o p p e r (I I) , co­
together w ith the approxim ate tim es required for balt ( I I ) , an d nickel (II) salts of ./V-phenylanthranilic
p recip itatio n to occur. acid were ashed an d the m etal was determ ined w ith
very good results. C arbon-hydrogen d ata w ere o b ­
tained fo r five com pounds p rep ared from ./V-methyl-
Acid Anion
Cation
iV-methyl A7-phenyl A7.iV-diphenyl iV-acetyl
an th ran ilic acid. T hree of these: co b alt(II), nickel(II),
and zinc (II) w ere identified by in fra red analysis as
Mg (II) 20 20 120 being co o rd in atio n com plexes; copper (II) and
yellow white white c a d m iu m (II) p ro d u cts w ere salts. The com plexes
C r(III) 20 i
yellow yellow w ith iro n (II) an d m anganese (II) w ere n ot analyzed.
M n(II) " 60 i 90 The calculated values are based on an anhy d ro u s
yellow pink gray
F e(II) i i i
com pound, and d ep artu res in the analytical results
orange brown tan (except fo r copper) indicate the presence of variable
F e (I II) i i i am ounts of w ater p ro b ab ly present as w ater of
violet brown orange
Co (II) i i 20 crystallization o r adsorbed w ater ra th e r th a n as co­
pink rose orchid o rd in ated w ater. T able II presents these data.
N i(II) i i i i
It blue yellow blue It blue
C u(II) i i i i Metal (II)
green brown green It blue Carbon H ydrogen
com plex
Z n(II) i i 20 i
peach It gray grav white or salt Calc. Found Calc. Found
Cd (II) i i 20 20 Co (II) 53.5 52.9 4.49 4.68
gray yellow gray gray N i(II) 53.5 52.7 4.49 4.65
C u(II) 52.8 49.1 4.43 4.34
Table I. Times of formation (in minutes) and colors of Z n(II) 52.6 52.7 4.41 4.62
precipitates of complexes and salts. Cd(II) 46.5 45.9 3.91 4.18

Table II. Selected carbon-hydrogen data for complexes

T he recovered m aterials w ere subjected to a
num ber of sim ple tests including solubility in a
variety of solvents both p o lar and n o n p o lar; these
included such com m on liquids as w ater, benzene,
carbon tetrachloride, ethanol, dioxane, diethyl ether
and p-xylene, as well as a num ber of less usual
solvents including dim ethyl form am ide, dim ethyl
sulfoxide, m esitylene, nitrotoluene, n-amyl acetate
and the dim ethyl ethers of diethylene glycol and
triethylene glycol. In no case was solubility in excess
of th at capable of p ro d u cin g a 1 0 ~ 3 m olar solution.
L im ited am ounts of m aterials w ere present, and no
attem pts were m ade to establish solubility p roduct
constants or other quantitative data.
of A^-methylanthranilic acid.
The p o o r agreem ent in the case of the copper (II)
salt m ay be attrib u ted to the in co rp o ratio n of con­
siderable am ounts of the o rig in al cation (n itrate) in
the lattice of the com plex leading to low results fo r
b oth carb o n and hydrogen.
As w ith the rin g substituted com pounds, the
/V-substituted an th ra n ilic acid anions acting as
ligands w ere checked by m eans of in fra red ab so rp ­
tion spectrophotom etry. Significant shifts to low er
w avenum bers in the 3 5 0 0 —3 3 0 0 cm -1 region and
in the 1100 — 1 0 0 0 cm -1 reg io n w ere used to es­
tablish presence of co o rd in atio n . The m agnitudes of

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 METAL ION COMPLEXES OF AROMATIC AMINO ACIDS II 529

these shifts w ere used to establish a relative o rd er of presented here because the sm all m ag n itu d e of the
stability fo r the com plexes, especially those in the shifts at the two im p o rtan t checking frequencies
N —H stretching region n ea r 3400 cm - 1 . P rin c ip a l w ere very sm all. No com plexes w ere obtained fro m
absorption peaks and relative shifts a re noted in reaction of the selected m etal cations w ith ./V-phenyl-,
T able III. D ata fo r the free acid and fo r the sodium ./VjTV-diphenyl-, and 7V-acetylanthranilic acids. On
salt are included. the basis of these in fra red shifts, a relative stab ility
sequence fo r the complexes of /V -m ethylanthranilic
Compound Principal absorption peaks [cm-1 ] acid was determ ined a s :
Fe (II) > Ni > Mn - Co > Zn .
iV-Methyl-
anthranilic T his series is som ew hat different th an those obtain ed
acid 3390 1660 1575 1510 1030
Sodium salt 3390 3000 1585 1550 1525 1035
w ith rin g substituted acids, and the fact th at iro n (II)
M n(II) form ed the strongest com plex in the ./V-methyl series
complex 3140 1590 1575 1550 1505 950 and was consistently am ong the w eaker com plexes
F e(II)
complex 3100 1590 1575 1535 1475 977 in the other series tends to obscure the p ictu re.
Co (II) P ossibly this phenom enon can be attrib u ted to bade
complex 3140 1600 1580 1540 1485 986 bon d in g enhanced by the presence of an electrophilic
N i(II)
complex 3110 1600 1550 1475 1005 gro u p on the am ino nitrogen p o rtio n of the chelate
Zn(II) ligand.
complex 3240 1620 1570 1515 1500 988
It should be noted th at the copper (II) salt of
TV-methylanthranilic acid was u n iq u e in its re la ­
Table III. Infrared absorption data for complexes of
jV-methylanthranilic acid. tively h igh solubility. Solutions of this salt w ere
intensely colored (green) at pn 6.5 or h igher. T his
The salts show ed much less p ro nounced shifts in salt in dilute solution m ight be useful as an acid-
the 3 4 0 0 cm -1 region, and the c o p p e r(II) and base in d icato r in the range 5.0 — 6.5.
cadm ium (II) salts h ad ad ditional peaks at 3 1 0 0 cm -1 A lthough stru ctu ral studies w ere n ot und ertak en ,
and 3020 cm -1 respectively sim ilar to th a t show n fo r it seems p ro b ab le th at the stru ctu res are squ are
sodium (I) at 300 0 cm -1 in Table I II . Shifts in the p la n ar and th at the ligand acts as a bidentate. In the
1000 cm -1 region were also characteristically sm all usually octahedral structures such as iro n (II) and
in com parison w ith those reported fo r the com ­ c o b a lt( I I) , coordinated w ater could occupy sites;
plexes. how ever, analytical d ata did not su p p o rt this con­
In frared data for the salts o btained from the clusion. The zinc (II) com plex is doubtless te tra ­
rem aining series of ^ -su b stitu ted acids are n o t hedral rath e r th an sq u are p lan ar.

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