Synthesis and characterization of titanium(IV), vanadium(III), chromium(III), and manganese(II) monobromoacetates and their complexes with organic bases

Article abstract of DOI:10.1081/SIM-100002233

Bromoacetates of the composition MX₃(OOCCH₂Br), MX₂ (OOCCH₂Br)₂, MX(OOCCH₂Br)₃, M(OOCCH₂Br)₄ (M = Ti), M(OOCCH₂Br)₃ (M = V, Cr), M(OOC

Full text of DOI:10.1081/SIM-100002233

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SYNTHESIS AND CHARACTERIZATION OF TITANIUM(IV),
VANADIUM(III), CHROMIUM(III), AND MANGANESE(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) SYNTHESIS AND CHARACTERIZATION OF TITANIUM(IV),
VANADIUM(III), CHROMIUM(III), AND MANGANESE(II) MONOBROMOACETATES AND THEIR COMPLEXES WITH ORGANIC BASES,
Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 31:3, 471-489, DOI: 10.1081/SIM-100002233
To link to this article: http://dx.doi.org/10.1081/SIM-100002233
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SYNTH. REACT. INORG. MET.-ORG. CHEM., 31(3), 471–489 (2001)
SYNTHESIS AND CHARACTERIZATION
OF TITANIUM(IV), VANADIUM(III),
CHROMIUM(III), AND MANGANESE(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 composition MX3(OOCCH2Br), MX2
(OOCCH2Br)2, MX(OOCCH2Br)3, M(OOCCH2Br)4 (M = Ti),
M(OOCCH2Br)3 (M = V, Cr), M(OOCCH2Br)2 (M = Mn) and
their complexes of the types MX2(OOCCH2Br)2.2B, M(OOCCH2
Br)4.2B(M=Ti, V), M(OOCCH2Br)3.B(M=Cr)andM(OOCCH2
Br)2.2B (M = Mn) (X = Cl, B = pyridine, quinoline, triethylamine
or 2-fluoroaniline) have been synthesized and characterized on the
basis of elemental analyses, infrared spectra, reflectance, molar
conductance and magnetic susceptibility studies.
INTRODUCTION
In continuation of our previous studies of solvolytic reactions in fused
monobromoacetic acid (1–7), the present investigation reports the synthesis of
∗Corresponding author. E-mail: jkpchem@rediffmail.com
471
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

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PURI, VATS, AND MIGLANI
monobromoacetatesoftitanium(IV), vanadium(III), chromium(III), manganese(II)
and their complexes with various bases. The nature of these solid compounds has
been established using physico-chemical methods.
The respective metal chlorides on refluxing in acetic acid gave anhydrous
metal acetates (8–9) of the composition OTi2(OAc)6 and [V3(OAc)8OH]. Many
contradictory reports exist in the literature (10–14) on the existence of vana-
dium(III) carboxylates of the compositions V(OOCH)3, V(OOCCH3)3.H2O,
V(OOCH)4, V(OOCH)3.HCOOH, V2(OOCCH3)6, V2(OOCC6H5)6, [V3(OH)
(OOCCH3)8], [V3(OH)(OOCC2H5)8], H+[V3O(OOCCH3)8]− and H+[V3O
(OOCC2H5)8]−. The formation of the compounds [Cr3(OH)(OOCCH3)8] has also
beenreported(9). Spath(15)haspreparedCr(III)acetatebyreactingchromium(III)
nitrate with acetic anhydride but subsequent studies (16) showed this compound
to be a trinuclear basic acetate, [Cr3(OH)2(OOCCH3)6H2O]+. The formation of
manganese(II) acetates, Mn(OOCCH3)2.4H2O, Mn(OOCCF3)2, Mn(OOCCl3)2
has also been reported in the literature (17–19).
RESULTS AND DISCUSSION
On solvolysis titanium(IV) chloride in monobromoacetic acid forms com-
pounds of the types TiCl3(OOCCH2Br), TiCl2(OOCCH2Br)2, TiCl(OOCCH2Br)3
and Ti(OOCCH2Br)4, respectively. The solvolysis reactions may be proposed as
follows
Fast Reaction
TiCl4 + CH2BrCOOH −−−−−→ TiCl3(OOCCH2Br) + HCl
Exothermic
Fast Reaction
TiCl3(OOCCH2Br) + CH2BrCOOH −−−−−→ TiCl2(OOCCH2Br)2+HCl
Slow Reaction
TiCl2(OOCCH2Br)2 + CH2BrCOOH −−−−−−→ TiCl(OOCCH2Br)3 + HCl
Reflux
TiCl(OOCCH2Br)3 + CH2BrCOOH −−−−−→ Ti(OOCCH2Br)4 + HCl
The stoichiometric compositions have been determined by elemental anal-
yses (Table I). All of these compounds have fairly high melting points and are
insoluble in most polar solvents with the exception of acetonitrile, dimethyl for-
mamide and nitrobenzene. Molar conductance values of their millimolar solutions
in these solvents exclude ionic dissociation.
Titanium Compounds
Infrared spectral studies of the solid monobromoacetates have been carried
out to elucidate their structures. The position of the asymmetric and symmetric

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473
stretching modes in the region 1400–1600 cm−1 have been used to determine
whether monobromoacetate behaves as monodentate or bidentate chelating bridg-
ing groups in a particular compound (20). In the case of TiCl2(OOCCH2Br)2 no
band has been observed in the region of 1720 cm−1 suggesting that no free car-
bonyl group is present. The intense absorption bands at 1585 and 1382 cm−1
suggest that the monobromoacetate groups in this compound are bidentate and
the central metal atom is hexa-coordinated. The bands observed at 1635 and 1590
cm−1 for TiCl2(OOCCH2Br)2, at 1645 and 1590 cm−1 for TiCl3(OOCCH2Br),
at 1640 and 1570 cm−1 for TiCl(OOCCH2Br)3 and at 1645 and 1575 cm−1 for
Ti(OOCCH2Br)4, respectively, suggest that some of the monobromoacetate groups
in all these compounds are acting as bridging groups as well (20). The other im-
portant bands present in the far-infrared spectra of the compounds are due to
metal-oxygen stretching modes. They are found in the region 500–340 cm−1. For
the titanium compounds Ti-O and Ti-Cl bands are observed in the regions 500–
350 cm−1 and 250–300 cm−1, respectively, and are given in Table II.
Vanadium Compound
Vanadium(III) chloride undergoes solvolysis in pure anhydrous monobro-
moacetic acid on refluxing to form a dull-green crystalline compound of the com-
position V(OOCCH2Br)3. This compound is insoluble in most common organic
solvents. Infrared spectral studies indicate bands at 1700, 1570 and 1260 cm−1
which may be assigned to asymmetric and symmetric COO− absorption bands
and which further indicate that the coordination of the metal atom is through both
oxygen atoms of the carboxylate group. The band observed in the lower region
i.e., 500–300 cm−1 may be assigned to the vanadium-oxygen bond.
The electronic spectra of V(OOCCH2Br)3 have also been recorded to shed
light on the nature of this compound. The electronic bands obtained at 11.11, 18.50
and 25.64 kK may be assigned to octahedral compounds of vanadium (III) in a
manner as reported earlier in the literature (21–24).
The compound V(OOCCH2Br)3 has been found to have a µeff value of 2.75
B.M. at room temperature which is in agreement with the literature values (2.5 to
2.8 B.M.) for V3+ ion in a cubic field. Consequently, the structure in Fig. 1 may
be proposed for this compound.
Chromium Compound
Similarly, a compound of the composition Cr(OOCCH2Br)3 has been pre-
pared from the solvolysis of anhydrous chromium(III) chloride with fused mono-
bromoacetic acid on refluxing. The new chromium(III) tris(monobromoacetate),

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PURI, VATS, AND MIGLANI

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PURI, VATS, AND MIGLANI
Table II. Important Infrared Spectral Bands of Transition Metal Bromoacetates and
Their Assignments in cm−1 Using Cesium Iodide Plates in Nujol
S.No.
Compound
νasymm(COO−)
νsymm(COO−) ν(M-O) ν(M-Cl)
(1)
TiCl3(OOCCH2Br) 1645 sb, 1590 s,
1565 s, 1530 m
1385 m
335 m
270 s
(2)
(3)
(4)
(5)
(6)
(7)
TiCl2(OOCCH2Br)2 1635 s, 1590 s, 1585 s
TiCl(OOCCH2Br)3 1640 s, 1570 s, 1535 m
1382 s
1400 w
1382 w
1260 s
1410 w
1295 s
405 s
490 s
360 m
420 s
525 m
430 s
280 s
280 s
—
—
—
Ti(OOCCH2Br)4
V(OOCCH2Br)3
Cr(OOCCH2Br)3
1645 s, 1575 s, 1540 m
1700 sb, 1570 s, 1555 m
1630 sb, 1550 s
Mn(OOCCH2Br)2 1680 sb, 1595 s, 1565 m
—
s = strong, sb = strong and broad, sh = shoulder, m = medium, w = weak.
Cr(OOCCH2Br)3, (d3system) is green, slightly hygroscopic and insoluble in com-
mon organic solvents like carbon tetrachloride, benzene and nitromethane, al-
though it is slightly soluble in acetonitrile and methanol.
The magnetic moment of the chromium(III) complex lies between 3.88 and
5.2 B.M. Since the 4A2g(F) state is the ground term, there is no orbital contribution
to the magnetic moment. Therefore, the µeff value should be close to the spin-only
value of 3.88 B.M. The experimental value for Cr(OOCCH2Br)3, is 3.64 B.M.
which is in the range expected for a d3 system (23).
Infrared spectral studies of this compound were made to understand the na-
ture of this compound in the solid state. The observed spectral bands along with
their assignments are shown in Table III. Band assignments for the carboxylate
group have been made by comparison with the spectra of the sodium salt of the
–
parent carboxylic acid (24,25). The C O stretching region of the compound is com-
plex which may be due to the formation of a polymeric structure in the solid state.
BrH2C
CH2Br
C
O
O
O
O
C
O
M
C
O
CH2Br
Figure 1. Suggested strucure of the complexes (M = V, Cr).

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477

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PURI, VATS, AND MIGLANI
Infrared bands at 1630 cm−1 and 1550 cm−1 have been attributed to νasymm(COO−)
whereas an absorption band at 1410 cm−1 has been assigned to νsymm(COO−). The
presence of more than one band due to the νasymm(COO−) stretching mode sug-
gests that the three carboxylato groups in this compound are non-equivalent and
may be unsymmetrically coordinated in the solid state. The ꢀν(COO−) value of
about 140 cm−1 may be attributed to the presence of bridging bidentate carboxylate
groups and this is quite likely in view of the tendency of chromium(III) to aquire
the coordination number six. Whereas the ꢀν(COO−) value of about 220 cm−1 is
larger than the expected value for a bidentate carboxylato group, such a high value
may either be due to unidentate or unsymmetrical bidentate carboxylato groups.
Two structural possibilities may be considered,
(i) The chromium in this compound may be four-coordinated, where four
of the six oxygen atoms of the three carboxylato groups are used to form
bonds. The three carboxylato groups would then be non-equivalent (one-
bidentate and two unidentate) and this would lead to the splitting of the
νasymm(COO−) band.
(ii) Or, alternatively, chromium in this compound may acquire six-coordina-
tion provided one of the carboxylato group is unsymmetrical with one
–
Cr O distance normal and the other significantly longer. The carbon-
oxygen bond order in Fig. 1 is consistent with the high value of the
νasymm(COO−) bond. The other two carboxylato groups may act as
symmetrical bidentate ligands probably exercising chelating or bridging
action.
The second possibility that chromium in this compound is six coordinated
seems more likely as Cr(III) is known to be always hexa-coordinated (26). This is
supported by the UV and visible spectra of this compound, Table II, which are typ-
ical of an octahedral environment about the Cr atom (26–27). The appearance of a
weak to medium intense band between 520-540 cm−1 in this compound has been
–
assigned to the ν(Cr O) stretching mode by analogy to a similar assignment in
trinuclear iron(III) acetate (28). The possibility that there are two types of carboxy-
lato groups is also consistent with the 1H NMR spectrum of Cr(OOCCH2Br)3. It
shows two peaks in the ratio 1:2 at δ10.1 and 12.1 ppm, respectively. The protons
in Cr(OOCCH2Br)3 are highly shielded which may be attributed to the presence
of unpaired electrons on the chromium metal. The 1H NMR spectra of the other
compounds could not be studied for lack of solubility in suitable solvents.
Manganese Compound
The compound Mn(OOCCH2Br)2 has been prepared similarly and studied
by infrared spectral studies. The bands at 1680, 1595 and 1295 cm−1 are due to

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479
asymmetric and symmetric ν(COO−) absorption bands which further indicate that
the coordination of the metal atom is through the oxygen atoms of the COO group.
The other important bands are given in Table II.
Electronic spectra have been recorded in support of the formation of the
compound Mn(OOCCH2Br)2 and are shown in Table V. They show weak absorp-
tion bands in the region 5.0–15 kK. No bands have been observed in the region
15.0–30.0 kK which rules out the possibility of tetrahedral derivatives (29). A dis-
tinction between tetrahedral and octahedral complexes could best be made from
the measurements of extinction coefficients. The octahedral complexes have a low
extinction coefficient of the order of 10−2–10−1 Lcm−1 mole−1, whereas for the
tetrahedral complexes, it lies between 1–10 Lcm−1mole−1
.
The extinction coefficients of the Mn(II) compound could not be evaluated
owing to their very low solubility in all conventional solvents. However, very
weak absorption bands obtained for the compound (Table V) are suggestive of an
octahedral environment around Mn(II) in an analogous manner as reported in the
literature (29,30). A band is observed at 33.33 kK for the compound which may
be assigned to charge transfer transitions.
The magnetic moment values for a high-spin octahedral derivative lie in the
range 5.68–6.10 B.M. whereas the values for a low-spin octahedral derivative range
from 1.8–2.1 B.M., the spin-only value for Mn(II) is expected to be 5.92 B.M. The
tetrahedral Mn(II) system possesses magnetic moments quite close to that, but
slightly higher than the spin-only value. The magnetic moment values calculated
for the Mn(II) compound (Table V) indicate this system to be consisting of five
unpaired electrons. It also rules out the possibility of a low-spin configuration.
Addition Compounds with Nitrogen Bases
Vanadium(III) and chromium(III) acetates are known to form complexes
with ammonia, pyridine, piperidine and dimethyl sulfoxide (31,32). Complex
derivatives of Mn(II) acetates have been reported with pyridine, γ -picoline,
pyridine-N-oxide and γ -picoline-N-oxide etc. in the literature (18). In the present
investigations, we have explored the possibility of the solvolysed products act-
ing as Lewis acids by reacting them with pyridine at room temperature in carbon
tetrachloride as a solvent, with continuous stirring for about 10 h using a magnetic
bead in case of the titanium(IV) bromoacetates (Table I). The representative equa-
tions for the formation of the base adducts of these titanium bromoacetates may
be suggested as:
CCl4
TiCl2(OOCCH2Br)2 + C5H5N −−−−−→ TiCl2(NC5H5)(OOCCH2Br)2
Stirring at
Room Temp.
for 10 h.

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PURI, VATS, AND MIGLANI
CCl4
Ti(OOCCH2Br)4 + 2C5H5N −−−−−→ Ti(NC5H5)2(OOCCH2Br)4
Stirring at
Room Temp.
for 10 h.
These compounds are soluble in dimethyl formamide. Molar conductance value
of their millimolar solutions are given in Table I. It is of interest to note that
there is no substitution of the less basic bromoacetate group by the more basic
pyridine and quinoline. In these compound, the separation of the symmetric and
– –
antisymmetric O C O band stretching frequencies and the shifts of the symmetric
– –
O C O stretching bands from the values in the parent compounds suggest that bro-
moacetate coordination becomes monodentate. The possibility of a five-coordinate
– –
structure for these compounds is ruled out as it would give two symmetric O C O
stretching bands. The probability of a polymeric structure is low on complex
– –
– –
formation with tertiary organic bases. The νasymm(O C O) and νsymm(O C O)
stretching frequencies shift to higher and lower frequency regions, respectively,
which suggests nitrogen donation to the central metal atom. Similar observations
have been reported by Kitchens and Bear (33).
Four vanadium complexes, V(OOCCH2Br)3.N(C2H5)3, V(OOCCH2Br)3.
NC5H5, V(OOCCH2Br)3.NC9H7 and V(OOCCH2Br)3.H2NC6H4F-2, have been
isolated in 1:1 molar ratio and characterised by elemental analyses. The represen-
tative equations for the formation of these complexes with bases may be shown
as
Reflux
V(OOCCH2Br)3 + B −−−−→ V(OOCCH2Br)3.B
in Benzene
for 20 h
=
[B C5H5N, C9H7N, (C2H5)3N, H2NC6H4F-2]
Their infrared spectra (Table III) contain all those bands which had been assigned
to internal vibrations of these bromoacetate groups in parent compounds and are
observed unperturbed. This may suggest that these bases are loosely solvated
and do not enter the coordination sphere possibly vanadium metal in all these
complexes has attained its highest coordination number. In case of the pyridine
adduct of vanadium bromoacetate, its infrared spectra shows bands at 1650 s,
1615 m, 1480 m, 1440 m, 1410 s, 1360 w, 1320 w, 1215 m, 1065 m, 1045 m,
1015 m, 965 w, 820 m, 750 m, 720 m, 690 m, 640 m, 600 sb, 525 m, 435 s,
410 m, 330 s, 245 w. The shift to higher frequency in the pyridine ring vibrations
(ν8a; 1615 cm−1, ν1 1010 cm−1, ν6a; 640 cm−1 and ν16b, 420 cm−1) suggests the
coordination of the pyridine ring nitrogen to vanadium. Bands which are assigned
to bromoacetate group in the spectrum of V(OOCCH2Br)3 are observed in the
spectrum of its adduct without any significant change (Table III). It again suggest
that the basic structure of this compound (Fig. 1) is not disturbed on coordination

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MONOBROMOACETATES AND THEIR COMPLEXES
481
by pyridine or any other base. However the structure of a base adduct of the above
metal bromoacetate with pyridine (B) in general may be suggested as:
All of these compounds are fairly soluble in most organic solvents. Elec-
tronic spectral studies of these addition compounds show bands at 10.8, 18.18,
26.31; 11.91, 17.98, 24.93; and 11.20, 18.34 and 27.62 kK, respectively which
also support the octahedral arrangement of vanadium(III). A band has also been
observed at 33.33 kK in these compounds, which may be assigned either to charge
transfer or to ligand absorption (Table IV). The ligand field parameters 10Dq and
β have also been evaluated employing energy ratio diagrams (34).
The addition compounds Cr(OOCCH2Br)3.NC5H5, Cr(OOCCH2Br)3.N
(C2H5)3, Cr(OOCCH2Br)3.NC9H7 and Cr(OOCCH2Br)3.H2NC6H4F-2 have also
been prepared in an analogous manner to that of the trinuclear basic Cr(III) acetate
complexes (35). The mode of formation of these complexes may be represented as
Reflux
Cr(OOCCH2Br)3 + B −−−−→ Cr(OOCCH2Br)3.B
in Benzene
for 20 h
=
[B C5H5N, C9H7N, (C2H5)3N, H2NC6H4F-2]
Table IV. Electronic Spectral (in kK 1000 cm−1 Units), Molar Coefficients ꢁ Values
(in L cm−1 mole−1) Given in Parentheses and Magnetic Moment Data of Vanadium(III)
Bromoacetates and Chromium(III) Bromoacetates and Their Complexes
µeff
a
Compound
ν1 (kK)
ν2 (kK) βꢁ (kK) ν3 (kK) 10Dq (kK) CT (B.M.)
V(OOCCH2Br)3
V(OOCCH2Br)3
.C5H5N
11.11 18.50(18) 0.560 25.64(12)
11.91 17.98(26) 0.558 24.93(34)
11.42
10.93
33.33 2.73
2.80
—
V(OOCCH2Br)3
.C9H7N
V(OOCCH2Br)3
.(C2H5)3N
11.20 18.34(30) 0.554 27.62(36)
10.80 18.18(34) 0.568 26.31(45)
11.51
11.47
33.33 2.82
33.33 2.71
µeff
b
ν1 (kK)
ν2 (kK) βꢁ (kK) ν3 (kK) 10Dq (kK) CT (B.M.)
Cr(OOCCH2Br)3 16.12(28) 22.72(16) 0.700 34.48(sh)
Cr(OOCCH2Br)3 15.98(43) 23.41(32) 0.723 35.22
16.12
15.98
3.64
3.67
.C5H5N
Cr(OOCCH2Br)3 16.66(53) 22.72(43) 0.595 38.48(sh)
.C9H7N
16.66
3.59
aObserved as shoulder on charge transfer band.
bAssignment obscured by charge transfer, ε molar value taken in methanol.

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PURI, VATS, AND MIGLANI
The infrared spectra of these addition compounds show all of the characteris-
tic bands which had been observed in their structures in which the basic framework
is not disturbed. Some new bands observed for Cr(OOCCH2Br)3.NH2C6H4F-2
–
may be attributed to ν(N H) stretching modes of the coordinated base. These
–
bands are at significantly lower frequency in comparison to the N H stretching
frequencies in the free base (Table III). The electronic spectra of Cr(OOCCH2Br)3,
Cr(OOCCH2Br)3.NC5H5, Cr(OOCCH2Br)3.NC9H7 have been studied and are
recorded in Table IV. The spectra of these compounds have all the features requisite
of an octahedral geometry.
Chromium(III) tris(monobromoacetate), Cr(OOCCH2Br)3, (d3 system) ab-
4
4
sorbs at 16.12 kK due to T2g ← A2g transitions (ν1) and 22.72 kK due to
4
4T1g ← A2g transitions (ν2) which are characteristic of a Cr(III) compound in
4
an octahedral ligand field (36). Unfortunately, the 4T1g(P)← A2g transition could
not be observed unambiguously since it appears as a weak shoulder on the main
charge transfer band. For chromium(III) bromoacetates, ν1 vibrations is a direct
measure of 10Dq. Also β1 values have been calculated from the energy ratio dia-
grams and from these observations the structure of their addition compounds with
bases may be suggested as shown in Fig. 2.
Similarly, the 10Dq values for Cr(OOCCH2Br)3, Cr(OOCCH2Br)3.NC5H5,
Cr(OOCCH2Br)3.NC9H7 were obtained at 16.12, 15.98 and 16.16 kK, respec-
tively. From the 10Dq values, β1 values of 0.700, 0.723, 0.595 cm−1 were obtained
for these compounds. The infrared spectra of the pyridine complex Cr(OOCCH2
Br)3.NC5H5 is complicated as was observed in the case of the analogous vana-
dium(III) compounds. The important infrared absorption bands for the compound
BrH2C
B
CH2Br
C
O
O
O
O
C
O
M
O
C
CH2Br
[M = Vor Cr; B = C5H5N, C9H7N, (C2H5)3N, H2NC6H4F]
Figure 2. Suggested structure of addition complexes of M(OOCCH2Br)3.

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483
Cr(OOCCH2Br)3.NC5H5 have been given in Table III. These bands may further be
explained in an analogous manner as already explained in the case of vanadium(III)
bromoacetates.
In the adduct Cr(OOCCH2Br)3.NC5H5 the same ν8a mode of pyridine (as
suggested earlier) cannot be distinguished clearly due to its overlapping with the νa
(COO−) stretching mode of the carboxylate group which occurs in the same region.
The band at 1010 cm−1 corresponds to the 991 cm−1 (ν1 mode) band of pyridine.
Other significant changes involve shifts to higher frequencies in ring vibrations of
the free pyridine at 601, 403 to 640 and 420 cm−1 in these complexes suggest the
coordination of the pyridine ring nitrogen to chromium. Bands which are assigned
to the monobromoacetate group in the spectrum of Cr(OOCCH2Br)3 are observed
in the spectrum of Cr(OOCCH2Br)3.NC5H5 without any significant shift. It again
suggest that the basic structure of this compound is not disturbed on coordination
with pyridine. These above spectral changes (Table III) clearly show that pyridine is
coordinated to the chromium atom. It is, therefore, inferred that monobromoacetato
chelates of vanadium(III) and chromium(III) have pseudooctahedral geometries
around the central metal ion. This is in agreement with the stereochemistry of
trivalent compounds of titanium, vanadium and chromium as reportd by Gutmann
and coworkers (37).
The adducts of Mn(OOCCH2Br)2 also have been prepared with pyridine,
triethylamine, quinoline and 2-fluoroaniline. The stoichiometric composition of
these adducts has been confirmed by their elemental analyses given in Table I. The
mode of representative equations for the formation of these adducts may be shown
as
Reflux
Mn(OOCCH2Br)2 + 2B −−−−−→[Mn(OOCCH2Br)2.B2]
in CCl4
for 12 h
=
[B C5H5N, C9H7N, (C2H5)3N, NH2C6H4 − F]
Their infrared spectra have also been recorded in the range 4000-200 cm−1
and the various bands and their assignments are recorded in Table III. The infrared
spectra of the amine complexes do not give a great deal of information on the
details of the structure. Octahedral pyridine metal halides give infrared bands in
the region assigned to a metal amine mode (38) and the present band is considered
to be derived from a variation of this type.
In the higher frequency region all the complexes gave strong absorption
bands in the ranges 1400-1500 cm−1 and 1500-1700 cm−1 due to symmetric
and asymmetric stretches, respectively, of the carboxylate group (Tables II and
III). The frequency difference between these bands has been previously used to
provide evidence for the bonding of the carboxylate group (39) but the results are

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484
PURI, VATS, AND MIGLANI
Table V. Electronic Spectral (in kK 1000 cm−1 Units) and Magnetic Moment Data of
Manganese(II) Bromoacetate and Its Complexes
Band Positions
d-d Transitions(kK)
Charge Transfer
Transition (kK)
µeff
Compound
(B.M.)
Mn(OOCCH2Br)2
5.88, 14.28
33.33
33.33
33.33
33.33
5.41
5.69
5.81
5.72
Mn(OOCCH2Br)2.2C5H5N
Mn(OOCCH2Br)2.2C9H7N
Mn(OOCCH2Br)2s.(C2H5)3N
6.41, 7.53 (12)
6.83, 13.21 (22)
6.91, 14.20 (28)
Molar values ε in L cm−1 mole−1 taken in methanol are given in parenthesis.
conflicting and are also sensitive to the nature of the substituents (40,25). From
these complexes it is clear that a group of complexes with similar stoichiometry
and presumably similar structure shows very similar values of ꢀν(difference in
νasymm and νsymm vibrations). The band near 860 cm−1, which has been described
–
(41) as a pseudosymmetric C C stretching mode, also seems to be metal sensitive.
Similar results to those previously reported (42,43) for copper pyridine complexes
were found for the other amine complexes.
The evidence in support of the formation of the above complexes has been
given by the electronic spectral studies. They show weak absorption bands in the
region 5.0-15.0 kK (Table V). No bands have been observed in the region 15.0
to 30.0 kK which rules out the possibility of a tetrahedral derivative and sug-
gest an octahedral arrangement in these complexes. A band obtained at 33.33 kK
in these complexes may be assigned to charge transfer spectra. The magnetic
susceptibility measurements gave values for the compounds Mn(OOCCH2Br)2,
Mn(OOCCH2Br)2.2NC5H5, Mn(OOCCH2Br)2.2NC9H7 and Mn(OOCCH2Br)2.
2N(C2H5)3 complexes as 5.41, 5.69, 5.81, and 5.72 B.M., respectively (Table V),
which further support the octahedral arrangement around the metal atom in these
complexes (Fig. 3)
B
O
O
O
O
BrH2C
C
C
CH2Br
Mn
B
Figure 3. Suggested structure for the addition complex.

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MONOBROMOACETATES AND THEIR COMPLEXES
EXPERIMENTAL
485
Materials and Methods
Monobromoacetic acid (Riedel, Germany) was crystallized in pure anhy-
drous benzene. The acid was then distilled under vacuum. Bromine was deter-
mined by the standard method known in the literature and its specific conductance
was found to be 1.35 × 10−3 ohm−1cm−1 which confirmed the purity of the bro-
moacetic acid. The melting point was also determined and bromoacetic acid with
m.p. 47–50 0C was used for all preparations.
A commercially available sample of titanium(IV) chloride was purified by
the standard method before use. Anhydrous vanadium(III) chloride was prepared
by refluxing powdered V2O5 (18.0 g, 0.1 mole) in 40 mL of sulfur monochlo-
ride for 8 h in the absence of moisture. Excess sulfur monochloride, which
contained dissolved sulfur, was decanted off and VCl3 thus formed was washed
with carbon disulfide. The violet product was filtered and dried under
vacuum at room temperature and analysed (Analysis % V: found 32.2; re-
quired 32.4 %; Cl found 67.4; required 67.6; yield obtained 13.55 g
(65%).
Anhydrous chromium(III) chloride was prepared and purified by the method
reported in the literature (44). The bromoacetates of titanium(IV) were prepared
by taking pure anhydrous samples of titanium(IV) chloride (2 g, 10.52 mmol)
in a standard joint flask fitted with a reflux condenser equipped with a silica
gel guard tube. To that was added pure anhydrous monobromoacetic acid (10 g,
71.94 mmol). The mixture was then refluxed in an oil bath maintained at the de-
sired temperature of the reaction for a period ranging from 24 h to a few days to
obtain maximum yields. The product thus formed was filtered under vacuum and
washed with anhydrous dichloromethane to completely remove excess of mono-
bromoacetic acid. The solvolysed product was dried under vacuum and analysed
(Table I).
Molar conductances of millimolar solutions were determined in acetoni-
trile, nitrobenzene or dimethyl formamide using a cell having a cell constant of
0.5996 cm−1 and a Beckmann RC-18 conductivity bridge.
Infrared and electronic spectra of the new compounds were measured in
nujol mull between cesium iodide plates using Perkin- Elmer 337 and 225 spec-
trophotometers. Solution spectra were obtained by using specially designed cells
with a 225 Analat-6160 FTIR system at St. Catherines University, Ontario, Canada.
Analyses of metals and halogens were carried out at the Chemistry Department,
Panjab University, Chandigarh, India, while the analyses of carbon, hydrogen and
nitrogen, were made by the Central Instrumental Laboratory at Panjab University,
Chandigarh, India.

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486
PURI, VATS, AND MIGLANI
Preparation of Bromoacetates
The bromoacetates V(OOCCH2Br)3, Cr(OOCCH2Br)3 and Mn(OOCCH2
Br)2 were prepared from VCl3 (5 g, 31.76 mmol) and monobromoacetic acid
(13.23 g, 31.76 mmol); CrCl3 (45.0 g, 28.4 mmol) and monobromoacetic acid
(11.83 g, 28.38 mmol); anhydrous MnCl2 (3 g, 23.79 mmol) and monobromoacetic
acid (6.61 g, 23.79 mmol), respectively, in separate round-bottomed flasks con-
taining 30 mL of carbon tetrachloride and fitted with a condensor and a guard
tube. The respective reaction mixtures were then refluxed in an oil bath for 30–
40 h. The green coloured product in case of the bromoacetates of vanadium and
chromium and the buff-coloured product obtained in case of manganese were then
filtered through a sintered glass filtration unit in a dry nitrogen atmosphere under
vacuum. The product was then washed with anhydrous hot benzene to remove
excess of bromoacetic acid from the product. Finally, the products were washed
with anhydrous dichloromethane and dried under vacuum and analysed (Table I).
Preparation of Adducts of Metal Bromoacetates with Bases
The addition compounds V(OOCCH2Br)3.NC5H5; V(OOCCH2Br)3.N(C2
H5)3; V(OOCCH2Br)3.NC9H7 and V(OOCCH2Br)3.H2NC6H4F-2 were prepared
by taking (1.5 g, 3.22 mmol) of V(OOCCH2Br)3 and (0.255 g, 3.22 mmol) of
C5H5N; V(OOCCH2Br)3 (1 g, 2.15 mmol) and (C2H5)3N (0.217 g, 2.15 mmol) and
V(OOCCH2Br)3 (1.0g, 2.15mmol)andC9H7N(0.277g, 2.15mmol);V(OOCCH2
Br)3 (1.2 g, 2.58 mmol) and H2NC6H4F-2 (0.286 g, 2.58 mmol), respectively,
in separate round-bottomed flasks containing 20 mL of benzene and equipped
with a guard tube. The respective bases were then added slowly to the respective
bromoacetates with continuous stirring using a magnetic stirrer. After complete
addition of the bases, the reaction mixture was allowed to reflux for about 20 h
between 70-750 C. The products were then filtered through a filtration unit in an
atmosphere of dry nitrogen under vacuum and finally the products were washed
with anhydrous dichloromethane and dried under vacuum13 and analysed (Table I).
The compound Cr(OOCCH2Br)3.NC5H5, Cr(OOCCH2Br)3.N(C2H5)3 and
Cr(OOCCH2Br)3.NC9H7, Cr(OOCCH2Br)3.H2NC6H4F-2, Mn(OOCCH2Br)2.
NC5H5, Mn(OOCCH2Br)2.N(C2H5)3, Mn(OOCCH2Br)3.NC9H7 and Mn(OOCC
H2Br)3.H2NC6H4F-2werepreparedbytakingCr(OOCCH2Br)3 (1.2g, 2.57mmol),
C5H5N (0.203 g, 2.57 mmol); Cr(OOCCH2Br)3 (1.4 g, 3.11 mmol), (C2H5)3N
(0.314 g, 3.1 mmol); Cr(OOCCH2Br)3 (1.2 g, 2.57 mmol), C9H7N (0.286 g, 2.57
mmol); Cr(OOCCH2Br)3 (1.5 g, 3.22 mmol), H2NC6H4F-2 (0.357 g, 3.22 mmol);
Mn(OOCCH2Br)2 (1.0 g, 3.62 mmol), C5H5N (0.573 g, 3.62 mmol); Mn(OOC
CH2Br)2 (1.35 g, 4.08 mmol), (C2H5)3N (0.824 g, 4.08 mmol); Mn(OOCCH2Br)2
(1.3 g, 3.93 mmol), C9H7N (1.01 g, 3.93 mmol) and Mn(OOCCH2Br)2 (1.4 g,

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MONOBROMOACETATES AND THEIR COMPLEXES
487
4.23 mmol), H2NC6H4F-2 (0.469 g, 4.23 mmol) were prepared by reacting the
respective bromoacetate and the base as described for the vanadium adducts.
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Received January 22, 1999
Accepted January 18, 2001
Referee I: K. Moedritzer
Referee II: D. Dollimore

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