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

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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

^aDepartment 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)₆and [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⁻¹have 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)₂no

band has been observed in the region of 1720 cm⁻¹suggesting 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⁻¹for TiCl₂(OOCCH₂Br)₂, at 1645 and 1590 cm⁻¹for TiCl₃(OOCCH₂Br),

at 1640 and 1570 cm⁻¹for TiCl(OOCCH₂Br)₃and at 1645 and 1575 cm⁻¹for

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⁻¹and 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⁻¹may be assigned to the vanadium-oxygen bond.

The electronic spectra of V(OOCCH₂Br)₃have 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)₃has been found to have a µ_effvalue 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)₃has 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⁻¹Using Cesium Iodide Plates in Nujol

S.No.

Compound

ν_asymm(COO⁻)

ν_symm(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)₂1635 s, 1590 s, 1585 s

TiCl(OOCCH₂Br)₃1640 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

—

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)₂1680 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 ⁴A_2g(F) state is the ground term, there is no orbital contribution

to the magnetic moment. Therefore, the µ_effvalue 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 d³system (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

C

O

M

C

O

CH₂Br

Figure 1. Suggested strucure of the complexes (M = V, Cr).

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PURI, VATS, AND MIGLANI

Infrared bands at 1630 cm⁻¹and 1550 cm⁻¹have been attributed to ν_asymm(COO⁻)

whereas an absorption band at 1410 cm⁻¹has been assigned to ν_symm(COO⁻). The

presence of more than one band due to the ν_asymm(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⁻¹may 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⁻¹is

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

ν_asymm(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

ν_asymm(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⁻¹in 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)₃are 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)₂has been prepared similarly and studied

by infrared spectral studies. The bands at 1680, 1595 and 1295 cm⁻¹are 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)₂and 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 10⁻²–10⁻¹Lcm⁻¹mole⁻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 ν_asymm(O C O) and ν_symm(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.NC₉H₇and 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

(ν_8a; 1615 cm⁻¹, ν₁1010 cm⁻¹, ν_6a; 640 cm⁻¹and ν_16b, 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)₃are 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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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.NC₉H₇and 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⁻¹Units), Molar Coefﬁcients ꢁ Values

(in L cm⁻¹mole⁻¹) Given in Parentheses and Magnetic Moment Data of Vanadium(III)

Bromoacetates and Chromium(III) Bromoacetates and Their Complexes

µ_eff

a

Compound

ν₁(kK)

ν₂(kK) β^ꢁ(kK) ν₃(kK) 10Dq (kK) CT (B.M.)

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

µ_eff

b

ν₁(kK)

ν₂(kK) β^ꢁ(kK) ν₃(kK) 10Dq (kK) CT (B.M.)

Cr(OOCCH₂Br)₃16.12(28) 22.72(16) 0.700 34.48(sh)

Cr(OOCCH₂Br)₃15.98(43) 23.41(32) 0.723 35.22

16.12

15.98

3.64

3.67

.C₅H₅N

Cr(OOCCH₂Br)₃16.66(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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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.NC₉H₇have 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, (d³system) ab-

4

sorbs at 16.12 kK due to T_2g← A_2gtransitions (ν₁) and 22.72 kK due to

4

⁴T_1g← A_2gtransitions (ν₂) which are characteristic of a Cr(III) compound in

4

an octahedral ligand ﬁeld (36). Unfortunately, the ⁴T_1g(P)← A_2gtransition could

not be observed unambiguously since it appears as a weak shoulder on the main

charge transfer band. For chromium(III) bromoacetates, ν₁vibrations is a direct

measure of 10Dq. Also β¹values 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.NC₉H₇were obtained at 16.12, 15.98 and 16.16 kK, respec-

tively. From the 10Dq values, β¹values of 0.700, 0.723, 0.595 cm⁻¹were obtained

for these compounds. The infrared spectra of the pyridine complex Cr(OOCCH₂

Br)₃.NC₅H₅is 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

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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MONOBROMOACETATES AND THEIR COMPLEXES

483

Cr(OOCCH₂Br)₃.NC₅H₅have 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.NC₅H₅the same ν_8amode of pyridine (as

suggested earlier) cannot be distinguished clearly due to its overlapping with the ν_a

(COO⁻) stretching mode of the carboxylate group which occurs in the same region.

The band at 1010 cm⁻¹corresponds to the 991 cm⁻¹(ν₁mode) 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⁻¹in 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)₃are observed

in the spectrum of Cr(OOCCH₂Br)₃.NC₅H₅without 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)₂also 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⁻¹and 1500-1700 cm⁻¹due 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

ORDER

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484

PURI, VATS, AND MIGLANI

Table V. Electronic Spectral (in kK 1000 cm⁻¹Units) and Magnetic Moment Data of

Manganese(II) Bromoacetate and Its Complexes

Band Positions

d-d Transitions(kK)

Charge Transfer

Transition (kK)

µ_eff

Compound

(B.M.)

Mn(OOCCH₂Br)₂

5.88, 14.28

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⁻¹mole⁻¹taken 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

ν_asymmand ν_symmvibrations). 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)₂.2NC₉H₇and Mn(OOCCH₂Br)₂.

2N(C₂H₅)₃complexes 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

BrH₂C

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 × 10⁻³ohm⁻¹cm⁻¹which 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 VCl₃thus 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⁻¹and 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)₃and Mn(OOCCH₂

Br)₂were 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.NC₉H₇and V(OOCCH₂Br)₃.H₂NC₆H₄F-2 were prepared

by taking (1.5 g, 3.22 mmol) of V(OOCCH₂Br)₃and (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 70-75⁰C. 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 vacuum¹³and analysed (Table I).

The compound Cr(OOCCH₂Br)₃.NC₅H₅, Cr(OOCCH₂Br)₃.N(C₂H₅)₃and

Cr(OOCCH₂Br)₃.NC₉H₇, Cr(OOCCH₂Br)₃.H₂NC₆H₄F-2, Mn(OOCCH₂Br)₂.

NC₅H₅, Mn(OOCCH₂Br)₂.N(C₂H₅)₃, Mn(OOCCH₂Br)₃.NC₉H₇and 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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Synthesis and characterization of titanium(IV), vanadium(III), chromium(III), and manganese(II) monobromoacetates and their complexes with organic bases

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