Syntheses and characterization of aluminium(III), iron(III), and copper(II) monobromoacetates and their complexes with organic bases

Article abstract of DOI:10.1081/SIM-100105262

Bromoacetates of the compositions Al(OOCCH₂Br)₃, AlBr(OOCCH₂Br)₂, FeCl(OOCCH₂Br)₂, FeCl₂(OOCCH₂Br) and Cu(OOCCH₂Br)₂ and M(OOCCH₂Br)

Full text of DOI:10.1081/SIM-100105262

This article was downloaded by: [Tulane University]
On: 08 October 2014, At: 03:49
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Synthesis and Reactivity in Inorganic and Metal-Organic
Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsrt19
SYNTHESES AND CHARACTERIZATION OF ALUMINIUM(III),
IRON(III), AND COPPER(II) MONOBROMOACETATES AND
THEIR COMPLEXES WITH ORGANIC BASES
J. K. Puri a , V. K. Vats a & Ashu Miglani a
a Department of Chemistry , Panjab University , Chandigarh, 160014, India
Published online: 15 Feb 2007.
To cite this article: J. K. Puri , V. K. Vats & Ashu Miglani (2001) SYNTHESES AND CHARACTERIZATION OF ALUMINIUM(III),
IRON(III), AND COPPER(II) MONOBROMOACETATES AND THEIR COMPLEXES WITH ORGANIC BASES, Synthesis and Reactivity in
Inorganic and Metal-Organic Chemistry, 31:6, 1063-1084, DOI: 10.1081/SIM-100105262
To link to this article: http://dx.doi.org/10.1081/SIM-100105262
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

SYNTH. REACT. INORG. MET.-ORG. CHEM., 31(6), 1063±1084 (2001)
SYNTHESES AND CHARACTERIZATION
OF ALUMINIUM(III), IRON(III), AND
COPPER(II) MONOBROMOACETATES
AND THEIR COMPLEXES
WITH ORGANIC BASES
J. K. Puri,* V. K. Vats, and Ashu Miglani
Department of Chemistry, Panjab University,
Chandigarh-160014, India
ABSTRACT
Bromoacetates of the compositions Al(OOCCH2Br)3,
AlBr(OOCCH2Br)2, FeCl(OOCCH2Br)2, FeCl2(OOCCH2Br)
and Cu(OOCCH2Br)2 and M(OOCCH2Br)3ÁB, M(OOC-
CH2Br)2Á2B, MBr(OOCCH2Br)2ÁB, MCl(OOCCH2Br)2Á2B,
MCl2(OOCCH2Br)ÁB. (MˆAl(III), Fe(III), Cu(II) and
B ˆ C5H5N, (C2H5)2NH, (C2H5)3N and NH2C6H4F have
been synthesized and characterized on the basis of elemental
analyses, infrared, re¯ectance, NMR spectral and magnetic
susceptibility studies.
*Corresponding author. E-mail: jkpchem@redi€mail.com
1063
Copyright # 2001 by Marcel Dekker, Inc.
www.dekker.com

1064
PURI, VATS, AND MIGLANI
INTRODUCTION
In continuation of our previous investigations of the behaviour of
various inorganic compounds, Lewis acids and bases and their solvolytic
reactions in the fused monobromoacetic acid solvent system178, we now
report the formation of bromoacetates of aluminium, iron, copper and their
complexes with various organic bases. The nature of these compounds has
been studied by various physical and spectroscopic techniques.
Metal chlorides have been shown to undergo solvolytic reactions in
acetic acid9. Anhydrous iron trichloride forms colourless crystals of the
type Fe3(OAc)6Cl3.AcOH while aluminium chloride and bromide form
compounds of the types Al(OAc)3.2AlO(OAc) and 2Al(OAc)3ÁAl-
Br(OAc)2.(C2H5)2O when solvolysed in acetic acid10,11. Monochloro-,
dichloro- and trichloroacetates of copper(II) have also been prepared and
their structures have been elucidated12.
EXPERIMENTAL
Materials and Methods used for Puri®cation and Characterization
Monobromoacetic acid was puri®ed by the reported method8.
Anhydrous metal halides were prepared by known methods before use8.
The organicbases were puri®ed by the usual methods. Monobromoacetic
anhydride was prepared by adding monobromoacetic acid (8.9 g, 64 mmol)
slowly to a 100 mL ¯ask containing 15.0 g of phosphorus pentoxide in
50 mL of CCl4 with thorough stirring in an atmosphere of dry nitrogen.
After complete addition of bromoacetic acid the mixture was then re¯uxed
at 70780 ꢀC for 12 hours. The reaction mixture was then ®ltered through
a ®ltration unit in an atmosphere of dry nitrogen. Finally, the residue was
repeatedly washed with anhydrous CCl4 and dried under nitrogen
atmosphere. Monobromoacetic anhydride (6.93 g, 26.67 mmol) was
obtained as white solid (melting point 56760 ꢀC, boiling point
1907197 ꢀC). The product was checked for the absence of phosphorus
and then crystallized from CCl4 as a shiny white solid in nearly 75%
yield. (CH2BrCO)2O [recrystallized]: melting point 58760 ꢀC, boiling
point 1907194 ꢀC [decomposed]: Found C, 18.15; H, 1.48; Br, 59.28,
Calculated for C4H4Br2O3: C, 18.46; H, 1.53; Br, 61.53%. IR (Nujol)
1880 s, 1780 sb, 1730 m, 1430 sh, 1260 mw, 1265 sb, 1215 s, 1115 sh, 1120 mw,
1085 vw, 1020 s, 1005 m, 920 m, 820 sb, 780 s, 650 s, 605 sh, 520 sh (where
s ˆ strong, sb ˆ strong and broad, sh ˆ shoulder, m ˆ medium, w ˆ weak,
vw ˆ very weak).

MONOBROMOACETATES
1065
The molar conductance of millimolar solutions were determined in
acetonitrile using a cell having a cell constant of 0.5996 cmÀ1 and a Beckman
(RC-18) conductivity bridge. Infrared spectra of the new compounds were
measured using cesium iodide plates with a Perkin Elmer 337 double beam
grating infrared spectrophotometer. The spectra of solid compounds were
recorded in Nujol mull. The proton NMR and 19F NMR spectra were
recorded on a Varian EM 390 (1H at 90 MHz, 19F at 84.16 MHz) in CDCl3
using TMS or Freon-11 as internal and external standards, respectively. The
electronic spectra of the solid compounds were recorded as di€use re¯ec-
tance spectra on a DMR-21 spectrophotometer at the Indian Institute of
Technology, New Delhi. The solution spectra of the complexes in diethyl
ether or methanol were scanned over a 2007800 nm range in 1 cm matched
quartz cells on a Beckmann D.B. UV and Vis spectrophotometer. Analyses
of carbon, hydrogen and nitrogen were made by the Central Instrumental
Laboratory of Punjab University, Chandigarh, and the analyses of halogens
and metals were made by the usual methods reported in the literature3.
Preparation of Al(OOCCH2Br)3, AlBr(OOCCH2Br)2, FeCl
-(OOCCH2Br)2, FeCl2(OOCCH2Br) and Cu(OOCCH2Br)2
The compounds Al(OOCCH2Br)3 and AlBr(OOCCH2Br)2 were pre-
pared by placing aluminium tribromide (2 g, 7.49 mmol) in two separate
round-bottomed ¯asks containing 20 mL of anhydrous carbon tetrachloride
and equipped with an anhydrous calcium chloride guard tubes. Bromoacetic
acid (3.12 g, 7.49 mmol and 2.08 g, 7.49 mmol), respectively, in 40 mL carbon
tetrachloride were added dropwise into these solutions slowly and the
reaction mixtures in both cases were re¯uxed for 24 h and 8 h, respectively,
in an oil bath. The solid products were ®ltered quickly through a sintered
glass ®ltration unit under a dry nitrogen atmosphere. The residues were
washed with hot benzene in order to remove the excess of bromoacetic acid
completely. The resulting products are white hygroscopic compounds. Their
compositions were established by elemental analyses (Table I).
The compounds FeCl(OOCCH2Br)2, FeCl2(OOCCH2Br) and
Cu(OOCCH2Br)2 were prepared by placing anhydrous ferric chloride (2 g,
12.30 mmol; 2.33 g, 14.38 mmol; or 1 g, 8.09 mmol) in separate round-bot-
tomed ¯asks containing 50 mL of carbon tetrachloride as solvent and
equipped with condensors and anhydrous calcium chloride guard tubes.
Bromoacetic acid (3.42 g, 12.30 mmol; 2 g, 14.38 mmol; or 2.25 g, 8.09 mmol)
were added slowly into the respective round bottomed ¯asks and the reac-
tion mixture in each case was re¯uxed in an oil bath for about 40 h
depending upon the completion of the reaction followed by the complete

1066
PURI, VATS, AND MIGLANI

MONOBROMOACETATES
1067
evolution of HCl gas during re¯uxing in each case. The solid products in
each case were ®rst ®ltered through a sintered glass ®ltration unit in a dry
nitrogen atmosphere to remove the solvent. The residue then was washed
with anhydrous dichloromethane and ®nally dried under vacuum. The
products were then analysed by elemental analyses (Table I).
The compounds Al(OOCCH2Br)3 and Cu(OOCCH2Br)2 were also
prepared by re¯uxing aluminium trioxide (0.5 g, 4.90 mmol) with mono-
bromoacetic anhydride (4.7 g, 18.8 mmol) and copper carbonate (0.6 g,
4.8 mmol) with monobromoacetic anhydride (18 g, 7.2 mmol) in 50 mL
carbon tetrachloride in a separate round-bottomed ¯ask equipped with a
condenser and anhydrous calcium chloride guard tube, respectively, for
8710 h at 70780 ꢀC. The resulting material in each case was ®rst ®ltered
through a sintered glass ®ltration unit in a dry nitrogen atmosphere to
remove excess solvent. The residue in each case was then washed with
anhydrous dichloromethane and ®nally the solid products were dried under
vacuum; Al(OOCCH2Br)3 (3.8 g, 8.62 mmol) was obtained as white solid in
nearly 86% yield and Cu(OOCCH2Br)2 (0.8 g, 3.98 mmol) was obtained as
bluish green solid (yield nearly 85%).
Preparation of Complexes of Al(OOCCH2Br)3, AlBr(OOCCH2Br)2,
FeCl(OOCCH2Br)2, FeCl2(OOCCH2Br) and Cu(OOCCH2Br)2
with C5H5N, (C2H5)2NH, (C2H5)3N, o-FC6H4NH2
and p-FC6H4NH2
The complexes of Al(OOCCH2Br)3 with C5H5N, (C2H5)2NH,
(C2H5)3N, o-FC6H4NH2 and p-FC6H4NH2 were prepared by treating
Al(OOCCH2Br)3 (1.85 g, 4.21 mmol) with C5H5N (0.33 g, 4.21 mmol);
Al(OOCCH2Br)3 (1 g, 2.26 mmol) with (C2H5)2NH (0.16 g, 2.26 mmol);
Al(OOCCH2Br)3 (1.09 g, 2.47 mmol) with (C2H5)3N (0.25 g, 2.47 mmol);
Al(OOCCH2Br)3 (1.33 g, 3.0 mmol) with o-FC6H4NH2=p- FC6H4NH2
(0.33 g, 3.0 mmol) in 20 mL benzene in round-bottomed ¯asks separately.
The mixtures were cooled in an ice bath while adding the respective base.
The respective mixture in each case was then brought to room temperature
and stirred for about 24 hours. Each solid product was then ®ltered through
a sintered glass ®ltration unit under an atmosphere of dry nitrogen, washed
with dichloromethane and dried under vacuum and analysed (Table II).
The complexes of AlBr(OOCCH2Br)2 with C5H5N, (C2H5)2NH,
(C2H5)3N, o-FC6H4NH2 and p-FC6H4NH2 were prepared similarly
by treating AlBr(OOCCH2Br)2 (1.21 g, 3.16 mmol) with C5H5N (0.25 g,
3.16 mmol); AlBr(OOCCH2Br)2 (1.31 g, 3.42 mmol) with (C2H5)2NH
(0.25 g, 3.42 mmol); AlBr(OOCCH2Br)2 (1.26 g, 3.30 mmol) with (C2H5)3N

MONOBROMOACETATES
1071
(0.33 g, 3.30 mmol); AlBr(OOCCH2Br)2 (1.15 g, 3.30 mmol) with o-FC6H4
NH2= p-FC6H4NH2 (1.15 g, 3.0 mmol).
The complexes of FeCl(OOCCH2Br)2, FeCl2 (OOCCH2Br) and
Cu(OOCCH2Br)2 with C5H5N, (C2H5)2NH, (C2H5)3N, o-FC6H4NH2 and
p-FC6H4NH2 were prepared in chloroform by treating FeCl(OOCCH2Br)2
(2.32 g, 6.329 mmol) with C5H5N (1.0 g, 6.329 mmol); FeCl2 (OOCCH2Br)
(1.67 g, 6.329 mmol) with C5H5N (0.50 g, 6.329 mmol); FeCl2 (OOCCH2Br)
(1.815 g, 6.849 mmol) with (C2H5)2NH (0.5 g, 6.849 mmol); FeCl2
(OOCCH2Br) (2.387 g, 9.00 mmol) with o-FC6H4NH2=p-FC6H4NH2 (1.0 g,
9.00 mmol); Cu(OOCCH2Br)2 (2.148 g, 6.329 mmol) with C5H5N (1.0 g,
6.329 mmol); Cu(OOCCH2Br)2 (0.80 g, 2.36 mmol) with (C2H5)3N ((0.47 g,
2.36 mmol); Cu(OOCCH2Br)2 (0.945 g, 2.78 mmol) with (C2H5)2NH
(0.350 g, 2.78 mmol); Cu(OOCCH2Br)2 (0.674 g, 1.98 mmol) with o-
FC6H4NH2 (0.220 g, 1.98 mmol) in the same manner as discussed above. All
these complexes were analysed (Table II) to establish their compositions.
RESULTS AND DISCUSSION
Metal Monobromoacetates
Aluminium Monobromoacetates
Aluminium monobromoacetates were prepared by the solvolytic
reactions of AlBr3 with monobromoacetic acid in 20 mL of carbon tetra-
chloride under re¯ux till the reactions are complete. Their mode of reactions
is as follows
CCl4
AlBr3 ‡ 3CH2BrCOOH À! AlꢁOOCCH2Br† ‡ 3HBr
CCl4
3
reflux 24 h
AlBr3 ‡ 2CH2BrCOOH À! AlBrꢁOOCCH2Br† ‡ 2HBr
2
reflux 8 h
Similarly, when Aluminium oxide is re¯uxed with monobromoacetic
anhydride in carbon tetrachloride it forms aluminium monobromoacetate
according to the equation;
CCl4
À!
Al2O3 ‡ 3ꢁBrCH2CO†2O
2AlꢁOOCCH2Br†
3
reflux 70À80ꢀC
The products obtained are listed in Table I and their stoichiometric com-
positions are con®rmed by their elemental analysis. All these aluminium
monobromaocetates are sparingly soluble in acetonitrile.

1072
PURI, VATS, AND MIGLANI
Infrared Spectra
Infrared spectral studies of these carboxylates have been carried out to
elucidate their structures. The positions of the asymmetric and symmetric
stretching modes in the region 140071600 cmÀ1 have been used to determine
whether monobromoacetate behaves as monodentate, bidentate-chelating
or bidentate-bridging group in a particular compound13. In the case of
Al(OOCCH2Br)3, the bands at 1660 cmÀ1 and 1580 cmÀ1 and in case of
AlBr(OOCCH2Br)2 the bands at 1655 and 1580 cmÀ1 may be assigned to
asymmetricand symmetricmodes of the carboxylate group ( Dn ˆ 80 cmÀ1
and 75 cmÀ1) shows that these groups are acting as bidentate chelating
groups14.
A polymeric structure for these carboxylates cannot be ruled out, but
the length of the polymer chain, may be quite short as these compounds
are known to be soluble in various aproticsolvents. In the acse of
Al(OOCCH2Br)3, no band that could be assigned to the n(Al-Br) stretching
mode is present which also suggests that all of the bromine atoms of
aluminium tribromide have been replaced by bromoacetate groups as a
result of complete solvolysis of aluminium tribromide with bromoacetic
acid. The infrared spectra of these compounds do not show any bands that
could be assigned to an O-H group, which indicates the absence of
free monobromoacetic acid. The various IR band assignments are shown
in Table III.
Table III. Important Infra-red Spectral Bands and Their Assignments (cmÀ1) of
Monobromoacetates of Aluminium, Iron and Copper in Nujol Using CsI Plates
Sr.
No. Compound
n(CH)
n(C-O)
n(C-C)
d(C-H)
(Aliphatic) n(CˆO) (Aliphatic) (Skeletal) (Aliphatic)
(1) Al(OOCCH2Br)3
2950 s
1660 s, 1220 s
1630 s,
1580 m
890 s
1410 m
(2) AlBr(OOCCH2Br)2 2940 s
(3) FeCl(OOCCH2Br)2 2925 s
(4) FeCl2(OOCCH2Br) 2930 m
1655 s, 1250 s
1580 m
900 s
890 s
890 s
895 s
1400 m
1400 m
1415 m
1440 w
1720 s, 1190 s,
1610 m 1130 m
1720 s, 1190 s,
1610 m 1150 m
(5) Cu(OOCCH2Br)2
2930 m
1715 s, 1210 s
1625 m

MONOBROMOACETATES
1073
Figure 1. Suggested structures of Al(OOCCH2Br)3 and AlBr(OOCCH2Br)2.
1H NMR Spectra
The 1H NMR spectra have been recorded to determine the position of
the methylene protons (Table VI). The spectra of Al(OOCCH2Br)3 and
AlBr(OOCCH2Br)2 in CDCl3 show singlets at 3.87 and 3.89 ppm attributed
to methylene protons.
Thus on the basis of the above studies the following probable struc-
tures may be assigned to these compounds.
Iron Monobromoacetates
Iron monobromoacetates were also prepared by the solvolytic reaction
of anhydrous ferric chloride with monobromoacetic acid in carbon tetra-
chloride at room temperature and on re¯uxing. Their mode of reactions
could be proposed as,
CCl4
FeCl3 ‡ CH2BrCOOH À! FeCl2ꢁOOCCH2Br† ‡ HCl
CCl4
2
room temp:
FeCl2ꢁOOCCH2Br†‡CH2BrCOOH À! FeClꢁOOCCH2Br† ‡HCl
2
roomtemp:
All these compounds are hygroscopic in nature and are soluble in nitro-
benzene, nitromethane and acetonitrile. Molar conductance value of their
millimolar solutions in acetonitrile indicate that they are fairly ionic com-
pounds.

1074
PURI, VATS, AND MIGLANI

MONOBROMOACETATES
1075

1076
PURI, VATS, AND MIGLANI
Infrared Spectra
The infrared spectra of these compounds show sharp bands at
1610 cmÀ1 due to symmetricbromoaectate groups. The other important
characteristic bands of these compounds are shown in Table III.
1H NMR Spectra
The 1H NMR spectrum of FeCl2(OOCCH2Br) in CDCl3 shows a singlet
at d 4.00 ppm attributed to methylene protons. The NMR spectrum of pure
monobromoacetic acid in CDCl3 shows a singlet at 3.94 ppm due to ÀCH2
protons and another singlet at 11.65 ppm due to ÀOH protons. The absence
of an ÀOH resonance and the shift in the methylene resonance in the spec-
trum of FeCl2(OOCCH2Br) con®rm the absence of free bromoacetic acid.
Electronic Spectra
The electronic spectrum of FeCl2(OOCCH2Br) shows weak bands at
6.25, 7.69 and 13.30 kK (Table V) while FeCl(OOCCH2Br)2 has weak bands
at 6.25, 12.50 and 14.30 kK (Table V). The absence of the bands in the
region 15.00730.00 kK rules out the possibility of a tetrahedral con®gura-
tion and thus indicates an octahedral arrangement around Fe(III). The band
at 41.67 kK is very intense and is assigned to a metal ligand charge transfer
band.
MagneticMeasurements
Magnetic
susceptibility
measurement
of
the
compounds
FeCl2(OOCCH2Br) and FeCl(OOCCH2Br)2 shown in Table V gave the
values 5.43 B.M. and 5.57 B.M. respectively, which also suggest an
octahedral arrangement for these compounds. Further light on the nature
of these compounds has also been shed from their adducts with organic
bases.
In the case of compounds FeCl2(OOCCH2Br) and FeCl(OOCCH2Br)2
the symmetricand the asymmetricstrethcing modes of the acrboxylate
group and iron thus acquires coordination number six. In the case of
compound FeCl(OOCCH2Br)2, iron acquires the coordination number of
six through chlorine bridging. Iron-chlorine stretching mode is observed at a
lower spectral region than observed for iron-chlorine (terminal) in the

MONOBROMOACETATES
1077
Table V. Electronic Spectral Data in kK (1000 cmÀ1 Units) e Molar Values in
Parentheses (in L cmÀ1 molÀ1) and MagneticMoment Data of Some Mono-
bromoacetates of Iron, Copper and Their Adducts
Charge transfer
transitions
kK
d-d Transitions
kK
meff
(B.M.)
Sr.No.
Compound
(1)
(2)
(3)
(4)
FeCl(OOCCH2Br)2 6.25, 12.50, 14.30
FeCl2(OOCCH2Br) 6.25, 7.69, 13.30 (8)
7
5.57
5.43
1.93
5.82
41.67
33.30
37.70
Cu(OOCCH2Br)2
FeCl(OOCCH2Br)Á
NH2C6H4F-o
11.49 (4), 15.38
6.67, 8.00, 11.10
(5)
(6)
(7)
(8)
(9)
(10)
FeCl2(OOCCH2Br)Á 7.69, 14.30 (43)
7
5.59
5.87
5.82
1.72
1.82
1.75
C5H5N
FeCl2(OOCCH2Br)Á 9.52
(C2H5)2NH
31.20, 40.00
FeCl2(OOCCH2Br)Á 6.67, 8.00, 11.10
37.70
7
NH2C6H4F-p
Cu(OOCCH2Br)2Á
2C5H5N
15.38 (57), 12.89
13.70 (65), 15.45
Cu(OOCCH2Br)2Á
7
2(C2H5)3N
Cu(OOCCH2Br)2Á
NH2C6H4F-o
12.80, 13.70 (43), 14.49, 33.30
terminal position. As the bridge metal-chlorine stretching modes are
expected to lie at lower spectral region than the terminal metal-chlorine
stretching modes, it is therefore reasonable to formulate the structure as
Fig. 2.
Copper(II) Monobromoacetates
Copper(II) monobromoacetates have been obtained by the solvolysis
of Cu(II) carbonate with either fused monobromoacetic acid or with the
anhydride of monobromoacetic acid according to the equations;
Reflux
CuCO3 ‡ CH2BrCOOH À! CuꢁOOCCH2Br† ‡ H2O ‡ CO2
2
in CCl4
70À80 ꢀ
Reflux
C
CuCO3 ‡ ꢁBrCH2CO†2O À! CuꢁOOCCH2Br† ‡ CO2
2
in CCl4
70À80 ꢀ
C

1078
PURI, VATS, AND MIGLANI
Figure 2. Suggested structure of FeCl(OOCCH2Br)2.
This compound is soluble in acetone but insoluble in ether, chloroform
and carbon tetrachloride and is hygroscopic.
Infrared Spectra
The structure of Cu(OOCCH2Br)2 has been elucidated spectro-
scopically. The infrared spectrum shows a strong band at 1715 cmÀ1 due to
asymmetric carboxylate stretching modes. A band of medium intensity is
observed at 1625 cmÀ1 assigned to symmetriccarboxylate absorptions. The
di€erence in asymmetric and symmetric carboxylate group frequencies
(Dn ˆ 90 cmÀ1) indicates that the ligand is acting as a bidentate chelating
ligand14. The spectrum also shows medium and weak bands at 2930 and
1440 cmÀ1 which are due to n(C-H) and d(C-H) (aliphatic) absorptions,
respectively (Table III). The electronic spectral and magnetic moment values
given in Table V suggests a square planar structure for the compound
Cu(OOCCH2Br)2 in an analogous manner to that reported in the literature16.
Thus, on the basis of above studies the following structure may be proposed as
Figure 3. Suggested structure for Cu(OOCCH2Br)2.

MONOBROMOACETATES
Lewis Base Adducts of Metal Monobromoacetates
1079
The preparation and spectral properties of bis(haloacetato)(b, b0,
b00triaminotriethylamine)cobalt(III) complexes have been reported in lit-
erature17. Melnik18 has reported the formation of binuclear ca€eine adducts
of Cu(II) acetate and Cu(II) chloroacetate. Kettle and his coworkers19 have
elucidated the structure of cupric acetate complexes with pyridine and a-
picoline. Copper(II) complexes of trichloroacetates with pyridine and qui-
noline have also been reported in the literature20. Lever and his coworkers16
have reported the complexes of tertiary organic bases with the haloacetates
of cobalt(II), nickel(II) and copper(II).
Complexes of Aluminium Bromoacetates with Bases
Complexes of aluminium bromoacetates with di€erent bases have
been prepared by the procedure discussed in experimental part. The repre-
sentative mode of reaction products of the metal bromoacetates with dif-
ferent organicbases may be proposed as
CCl4
À!
AlꢁOOCCH2Br† ‡ B
AlꢁOOCCH2Br†3ÁB
3
stirred for ꢂ 24 h
at room temp:
AlBrꢁOOCCH2Br† ‡ B
À!
AlBrꢁOOCCH2Br†2ÁB
2
stirred for ꢂ 24 h
at room temp:
‰B ˆ C5H5N; ꢁC2H5†2NH; ꢁC2H5†3N; NH2C6H4FŠ
Infrared Spectra
The infrared spectra of the adducts Al(OOCCH2Br)3. NC5H5 and
AlBr(OOCCH2Br)2. NC5H5 show a large number of IR bands and the
discussion is centred mainly around those absorptions which have
structural signi®cance. Absorptions of medium intensity at 1630 cmÀ1 are
due to asymmetric carboxylate absorptions. The di€erence in the asym-
metric and symmetric carboxylate group frequencies (Dn ˆ 100 cmÀ1
)
indicate that the ligand is acting as a bidentate chelate. The spectra of
these adducts also show bands of medium to weak intensity at 3140, 1455
and 1395 cmÀ1 which are ascribed to n(C-H) (aromatic), n(C-C) (skeletal)
and d(C-H) (aliphatic) frequencies. The appearance of a band at 780 cmÀ1
due to n(Al-N) indicates the coordination of the nitrogen of the pyridine

1080
PURI, VATS, AND MIGLANI
to the central metal atom. The bands observed at 725 and 675 cmÀ1 may
be due to n(C-N) vibrations and n(C-H) (aromatic) bending modes,
respectively.
The infrared spectral studies of the analogous diethylamine adducts,
Al(OOCCH2Br)3ÁNH(C2H5)2 and AlBr(OOCCH2Br)2ÁNH(C2H5)2, also
indicate an absorption of medium intensity at 1640 cmÀ1 which is due to
the carboxylate asymmetric stretching mode. A band of medium intensity
is observed at 1535 cmÀ1 which is due to the carboxylate symmetric
stretching mode. The di€erence in asymmetric and symmetric carboxylate
group frequency (Dn ˆ 95 cmÀ1) indicates that the ligand is bidentate and
chelating13. The other characteristic bands of these adducts are shown in
Table IV.
The adducts Al(OOCCH2Br)3.N(C2H5)3 and AlBr(OOCCH2Br)2Á
N(C2H5)3 were also prepared and characterized by their elemental ana-
lyses (Table II) and infrared spectral studies. The infrared spectra display
an absorption of medium intensity at 1530 cmÀ1. The di€erence in
asymmetric and symmetric carboxylate group frequency indicates that the
ligand is bidentate and chelating14. The appearance of a band at
760 cmÀ1 due to the Al-N absorption indicates the coordination of
nitrogen of triethylamine with aluminium metal. The relevant bands
are recorded in Table IV. The adducts Al(OOCCH2Br)3ÁH2NC6H4F-o,
AlBr(OOCCH2Br)2ÁH2NC6H4F-o, Al(OOCCH2Br)3ÁH2NC6H4F-p and
AlBr(OOCCH2Br)2ÁH2NC6H4F-p, have also been prepared and were
1
characterized by their elemental analyses, infrared spectral and H NMR
studies (Tables II, IV, V and VI).
Complexes of Iron Bromoacetates with Bases
Complexes of the compositions FeCl(OOCCH2Br)2Á2NC5H5,
FeCl2(OOCCH2Br)ÁNC5H5, FeCl2(OOCCH2Br)ÁNH(C2H5)2, FeCl2(OOC-
CH2Br)ÁH2NC6H4F-o and FeCl2(OOCCH2Br)ÁH2NC6H4F-p have also
been prepared and analysed as shown in Table II. The representative mode
of reaction for these addition complexes may be proposed as shown below.
CCl4
FeClꢁOOCCH2Br† ‡ 2B
À!
stirred at room temp:
forꢂ24 h
FeClꢁOOCCH2Br†2ÁB2
2
CCl4
FeCl2ꢁOOCCH2Br† ‡ B
À!
FeCl2ꢁOOCCH2Br†ÁB
stirred at room temp:
forꢂ24 h
‰B ˆ C5H5N; ꢁC2H5†2NH†; NH2C6H4F-o=NH2C6H4F-pŠ

MONOBROMOACETATES
1081
Table VI. The Proton and 19F NMR Data of Monobromoacetates of Iron,
Aluminium and Copper and Their Adducts with Bases
Chemical Shifts
(ppm) C5H5N=
Et2NH=Et3N=
o=p NH2C6H4F
19F
Chemical
Shift
S. No.
Compounds
(OOCCH2Br)
(ppm)
(1)
(2)
(3)
(4)
Al(OOCCH2Br)3
AlBr(OOCCH2Br)2
FeCl2(OOCCH2Br)
Al(OOCCH2Br)3Á
C5H5N
3.87 (s)
3.89 (s)
4.00 (s)
3.88
(s, 6H)
3.90
(s, 6H)
7
7
7
7
7
7
7
8.45 (d, 2H),
7.65 (m, 3H)
1.20 (t, 6H),
3.0 (q, 4H)
(5)
Al(OOCCH2Br)3Á
7
(CH3CH2)2NH
0.62 (s, NH, H)
1.20 (t, 9H),
3.46 (q, 6H)
7.20 (m, 4H),
3.65 (s, NH2, 2H)
7.20 (m, 4H),
3.70 (s, NH2, 2H)
8.45 (d, 2H),
7.65 (m, 3H)
1.20 (t, 6H),
3.60 (q, 4H),
0.62 (s, NH, H)
1.20 (t, 9H),
3.46 (q, 6H)
7.20 (m, 4H),
3.65 (s, NH2, 2H)
7.20 (m, 4H),
3.70 (s, NH2, 2H)
8.40 (d, 4H),
7.65 (m, 6H)
8.47 (d, 2H),
7.65 (m, 3H)
1.51 (t, 6H),
3.12 (q, 4H),
0.62 (s, NH, H)
6.92 (m, 4H),
3.65 (s, NH2, 2H)
7.26 (m, 4H),
3.65 (s, NH2, 2H)
8.42 (d, 4H),
7.65 (m, 6H)
(6)
(7)
(8)
(9)
(10)
Al(OOCCH2Br)3Á
(CH3CH2)3N
3.85
(s, 6H)
3.90
(s, 6H)
3.91
(s, 6H)
3.90
(s, 4H)
3.90
(s, 4H)
7
Al(OOCCH2Br)3Á
À130.70
À130.50
7
NH2C6H4F-o
Al(OOCCH2Br)3Á
NH2C6H4F-p
AlBr(OOCCH2Br)2Á
C5H5N
AlBr(OOCCH2Br)2Á
(CH3CH2)2NH
7
(11)
(12)
(13)
(14)
(15)
(16)
AlBr(OOCCH2Br)2Á
(CH3CH2)3N
3.85
(s, 4H)
3.90
(s, 4H)
3.91
(s, 4H)
3.92
(s, 4H)
3.92
7
AlBr(OOCCH2Br)2Á
À130.70
À130.50
7
NH2C6H4F-o
AlBr(OOCCH2Br)2Á
NH2C6H4F-p
FeCl(OOCCH2Br)2Á2
C5H5N
FeCl2(OOCCH2Br)Á
C5H5N
7
(s, 2H)
3.62
(s, 2H)
FeCl2(OOCCH2Br)Á
7
(CH3CH2)2NH
(17)
(18)
(19)
FeCl2(OOCCH2Br)Á
NH2C6H4F-o
4.10
(s, 2H)
3.98
(s, 2H)
5.10
(s, 4H)
À136.30
À136.50
7
FeCl2(OOCCH2Br)Á
NH2C6H4F-p
Cu(OOCCH2Br)2Á
2C5H5N

1082
PURI, VATS, AND MIGLANI
Infrared Spectra
The infrared spectra of all these compounds have been measured and
the important characteristic bands of all these compounds have also been
assigned in Table IV. The di€erence in asymmetric and symmetric carbox-
ylate group frequency in all of these adducts indicate that the ligands are
bidentate and chelating14.
1H NMR and 19F NMR Spectra
1
1
The chemical shifts obtained from H NMR and F NMR spectra in
all these compounds tabulated in Table VI also suggest the formation of
these compounds. The electronic and magnetic susceptibility data of all
these adducts shown in Table V also suggest an octahedral arrangement
around iron(III).
Complexes of Copper(II) Monobromoacetates with Bases
The addition complexes of the compositions Cu(OOCCH2Br)2Á2N-
C5H5, Cu(OOCCH2Br)2ÁNH(C2H5)2, Cu(OOCCH2Br)2ÁN(C2H5)3 and Cu-
(OOCCH2Br)2ÁH2NC6H4F-o have also been prepared by the general method
as shown in case of iron and aluminium complexes and characterized by
their elemental analyses shown in Table II. The infrared spectra of these
compounds indicate strong absorptions bands at 1720, 1615, 1625 and
1610 cmÀ1, respectively, due to n asymmetric carboxylate stretching modes.
The other characteristic spectral bands at 1450, 2840, 2340 and 1420 cmÀ1
are due to n(C-H) (aromatic), n(C-H) (aliphatic) and d(C-H) (aliphatic)
absorptions. Infrared spectra do not show the presence of any band that
could be assigned to an OH group indicating that no free monobromoacetic
acid is present in these adducts.
The magneticmoment values listed in Table V for all these complexes
show either six-coordinate octahedral structures (possibly distorted) or four-
coordinated square-planar complexes since in both cases, there is no orbital
contribution to the moment apart from that coordinated in second order by
spin-orbit coupling as explained earlier in the literature19. Four-coordinate
2
tetrahedral structures can be eliminated as these would have a T2 ground
state and would be expected to have moments greater than 2.0 B.M. The
re¯ectance spectra are consistent with either a square-planar (monodentate
bromoacetate) or a severely tetragonally distorted octahedral structure in an

MONOBROMOACETATES
1083
Figure 4. Suggested structure for Cu(OOCCH2Br)2Á2B (B=Base).
analogous manner already reported in the literature21. However, in general
the structure for the adducts may be proposed as in Fig. 4.
REFERENCES
1. Puri, J.K.; Kaur, J.; Sharma, V.; Miller, J.M. SolvolyticBehaviour and
Solubilities of Various InorganicCompounds. Lewis Acids and Bases
in Monobromoacetic Acid. Polyhedron 1983, 2, 128771292.
2. Puri, J.K.; Vats, V.K.; Mandal, H.; Miller, J.M. SolvolyticReactions
of Lewis Acids in Monobromoacetic Acid and the Nature of the
Solvolysed Products. Inorg. Chim. Acta 1985, 97, 2057208.
3. Puri, J.K.; Kaur, J.; Sharma, V.; Miller, J.M. Preparation of Metal
Bromoacetates from other Salts by Solvolytic Reactions in Fused
Monobromoacetic Acid. Polyhedron 1985, 4, 125371257.
4. Puri, J.K.; Miller, J.M. Solvolytic Reactions of Lewis Acids in
Dibromoacetic Acid and the Characterization of the Solvolysed Pro-
ducts. Inorg. Chim. Acta. 1985, 101, 1357140.
5. Puri, J.K.; Vats, V.K.; Sharma, V. Oxidation-Reduction Reactions
and Analysis of Thiourea, Hydrazine and Ascorbic acid in Mono-
bromoacetic Acid. Indian J. Chem. 1986, 25, 5657570.
6. Puri, J.K.; Vats, V.; Miglani, A.; Khattar, R.; Rehani, S.K. Synthesis
and Characterization of Aluminium(III), Iron(III) and Copper(II)
Monobromoacetates and their Complexes with Organic Bases. Pre-
sented at the International Chemistry Symposium held at Manchester
University: Hamilton, Ontario, Canada, 1989; June 11713.
7. Puri, J.K.; Sharma, V.; Vats, V.K. Physico-Chemical Studies of Var-
ious Protonic Acids, Bases and Salts in Monobromoacetic Acid. Pre-
sented at the Fifth Annual Conference of the Indian Council of
Chemists at Sindri (Dhanbad): India, 1985; Abstract IP-29.

1084
PURI, VATS, AND MIGLANI
8. Puri, J.K.; Vats, V.K.; Miglani, A. Synthesis and Characterization of
Titanium(IV), Vanadium(III), Chromium(III) and Manganese(II)
Monobromoacetates and their Complexes with Organic Bases. Synth.
React. Inorg. and Met. Org. Chem. 2000, Submitted after Revision.
9. Griswold, E.; Olson, F.V. Solubility Relations in the System Lead
Acetate-Sodium Acetate, Acetic Acid at 30ꢀ. J. Amer. Chem. Soc.
1937, 59, 189471895.
10. Funk, H.; Demmel, M. The Reaction of Anhydrous Ferric Chloride
with Anhydrous Acetic and Formic Acids. Z. Anorg. Allgem. Chem.
1936, 227, 947102.
11. Funk, H.; Schormuller, J. Acetates of Aluminium Chloride and Bro-
mide. Z. Anorg. Allgem. Chem. 1931, 199, 93796.
12. Patel, K.S.; Faniran, J.A.; Earnshaw, A. Magneticand IR Studies of
Copper(II) Chloroacetates. J. Inorg. Nucl. Chem. 1976, 38, 3537356.
13. Nakamoto, K. Complexes of Carboxylic Acids, Oxy Acids and
Alcohols. In Infrared Spectra of Inorganic and Coordination Com-
pounds; Ed.; John Wiley and Sons: New York, 1963; 1977201.
14. Faniran, J.A.; Patel, K.S.; Mesubi, M.A. Physico-Chemical Studies of
Metal Haloacetates III. Infrared Spectra of Crystalline Divalent Metal
Dichloroacetates. Spectrochim Acta. 1975, 31A, 1177122.
15. Furlani, C.; Furlani, A. Absorption Spectra of Some Tetrahalogeno-
Manganates(II). J. Inorg. Nucl. Chem. 1961, 19, 51754.
16. Lever, A.B.P.; Ogden, D. Haloacetate Complexes of Cobalt(II),
Nickel(II) and Copper(II) and the Question of Band Assignments in
the Electronic Spectra of Six Coordinate Cobalt(II) Complexes.
J. Chem. Soc. (A) 1967, 204172048.
17. Kuo, K.W.; Madan, S.K.; Stanley, K. The Preparation and Spectral
Properties of Bis(halogenoacetato)(b,b0,b00-triaminotriethylamine)-
cobalt(III) Complexes. Inorg. Chem. 1969, 83, 158071584.
18. Melnik, M. Binuclear Ca€eine Adducts of Copper(II) Acetates and
Copper(II) Chloroacetates with Unusually High Antiferromagnetic
Interaction. J. Inorg. Nucl. Chem. 1981, 41, 303573038.
19. Kettle, S.F.A.; Pioli, A.J.P. CupricAcetate Complexes of Pyridine and
Picoline. J. Chem Soc. (A) 1968, 124371247.
20. Amasa, S.; Brown, D.H.; Sharp, D.W.A. Amine and Amine N-Oxide
Complexes of First-Row Transition-Metal Tri¯uoroacetates and Tri-
chloroacetates. J. Chem. Soc. (A) 1969, 289272894.
21. Kato, M.; Jonassen, H.B.; Fanning, J.C. Copper(II) Complexes with
Some Normal MagneticMoments. Chem. Rev. 1964, 64, 997125.
Received November 9, 1998
Accepted May 13, 2001
Referee I: M. R. Malachowski
Referee II: R. F. Jordan