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Synthesis and Characterisationof Bis(η5-Fluorenyl)N,N-disubstituted-dithiocarbamatochlorotitanium(IV)and Zirconium(IV) CompondsAnand K. Sharma a & N. K. Kaushik aa Department of Chemistry , University of Delhi ,Delhi, 110007, IndiaPublished online: 05 Dec 2006.

To cite this article: Anand K. Sharma & N. K. Kaushik (1981)Synthesis and Characterisation of Bis(η5-Fluorenyl)N,N-disubstituted-dithiocarbamatochlorotitanium(IV) and Zirconium(IV) Componds, Synthesisand Reactivity in Inorganic and Metal-Organic Chemistry, 11:7, 685-693, DOI:10.1080/00945718108056013

To link to this article: http://dx.doi.org/10.1080/00945718108056013

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SYNTH. REACT. INORG. MET.-ORG. CHFN., 11(7), 685-693 (1981)

SYNTHESIS AND CHARACITRISATION OF B I S ( ~ s - F L U O R e m ) N , N - D I S J B S T ~ -

DITHIoCAReAMAToCHLORoTITANIUM(IV) AND ZIRCONIUM(IV) COMPWNDS

ANAND K.SHARMA and N.K.KAUSHIK*

Department of Chemistry, University of Delhi, Delhi-110007 (India)

ABSTRACT

Some bis(9 -fluorenyl)N.N-disubstituteddithiocarb~atochloro- 5

5 titanium(1V) and zirconium(1V) compounds of the type ( 7 -C13H,),Ti(S,CNRR1)C1 and (7 -C,3H,)2Zr(S2CNRRv)C1 (where R = alkyl and R ' = aryl or cyclohexyl)

have been prepared by the reaction of bis ( ~5-fluorenyl)titaniun(IV)dichloride

and bis(

N,N-disubstituted dithiocarbamates. A study of molecular weight, conductance,

infrared spectra and magnetic susceptibility in addition to elemental

analysis has been carried out to throw some light on the probable structure

of these derivatives. These studies show that the complexes are monomeric,

non-electrolytes in which the dithiocarbamate group acts as a bidentate

ligand.

5

fluorenyl)zirconium(IV)dichloride with the sodium salt of 9"-

INTRODUCTION

Dithiocarbaeate ligands of some early transition metals are reported

in various coordination states. For instance, 8-coordination occurs in

Ti(S2CNR2J4' and Zr(S2CNR2)42, 7-coordination in TiCl(S2CNR2)3 , CpZr(S2CNR2)3 1 3

68 5

Copyright 0 1981 by Marcel Dekker, Inc

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686 SHARMA AND KAUSHIK

1 and WeCpZr (S2CNR2) 34, 6-coordination in C12Ti (S2CNR2)2 . Some 5-coordinated

metal dithiocarbamates have also been reported. For instance, Coutts et al.

have reported the preparation of CpTi(S2CNR2)2 , and CpTi(S2CNR2)C12 . Kaushik et a1 . have synthesised CpZTi (S2CNR2)C17, Cp2M(S2CNHR)C18s9 and

MeCp2 (SzCNHR)Cllo (where M a titanium or zirconium). They have described

bidentate nature of the dithiocarbamate ligands in all these complexes.

there is no information in the literature about the complexes of the type

5 6

As

(7 5 C13Hg)2TifS2ChQR')C1 and ( ?f-C,,Hg)2Z~(S2CNRR')C1 (where R = CH3, C2H5,

C3H, and R' = C6Hs, C H

The main interest in the preparation of such compounds is the attachment of

dithiocarbamate ligand to the titanium and zirconium metal in presence of

bulky fluorenyl groups which due to some steric factors might havc sonc

effect on the structure OC com2lexes.

been found to have bidentate dithiocarbarnate ligands, similar to those

reported earlier .

) we have prepared and characterised these compounds. 6 11

However, these conipounJs have also

1-13

RESULTS AND DISCUSSION

It i s evident From analytical data that one mole of bi~(~~-fluorenyl)-

titanium(1V)dichloride or bis (~5-fluorenyl)zirconium(IV)dichloride reacts

with one mole of sodium dithiocarbamate according to the following equation

( ~\~-C,,H,)~MC~~ + Na(S2CNRR') __j

(M = Ti(IV), Zr(1V); R = alkyl and R' = aryl or cyclohexyl)

( ~s-Cl,H,)2hl(S2CNRR~)C1 + NaCl

The method described above gives products of high purity as can be

judged by their elemental analysis, molecular weight determination and i,r.

spectral data.

Conductance measurements show that all the complexes are non-electrolytes

From molecular weight measurements it is concluded that these in nitrobenzene.

complexes are monomeric.

show that all are diamagnetic.

Magnetic susceptibility values of these complexes

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TITANIUM (IV) AND ZIRCONIUM (IV) COMPOUNDS 687

All these complexes are quite stable as solids in an inert atmosphere

and also in dry air, but decomposes in the presence of moisture.

compounds are soluble in methanol, ethanol and benzene and are insoluble in

chloroform, carbon disulphide, dichloromethane and acetone.

The

In recent years the infrared spectra of numerous dithiocarbamates have

Fortu- been reported 2’14’15.

nately from a structural point of view, it is only necessary to distinguish

between unidentate and bidentate dithiocarbamate groups.

lities can be distinguished by infrared spectral studies.

showed that if the dithiocarbamate ligand is bidentate, a single band at

y 1000 cm-l is found which is due to two equivalent C-S stretching

In general, these spectra are fairly complex.

These two possibi- 14 Bonati and Ugo

vibrations,

doublet arises at N 1005 and 983 cm-’ which is due to two non-equivalent C - S

stretching vibrations.

intensity band 1000 at-’ (apart from C-H deformation band, characteristic of

all n-fluorenyl derivatives). This indicates the presence of a four-membered

ring system in the complexes and supports the bidentate nature of the

dithiocarbamate ligands.

In the case of unidentate dithiocarbamates, as in EtS2CNEt2, a

All the complexes prepared possess one medium

Table I. lists the characteristic infrared frequencies of the compounds.

Bands occurring around - 1510, v 380 and - 360 cm-’ in these complexes have been assigned to 3 ( C - L N ) , 3@-Cl) and 3W-S) vibrations, respectively.

The bands occurring at N 3100, ,Q 1440, r~ 1025 and N 810 cm-l in all these

compounds show the presence of 77-bonded fluorenyl groups.

The electronic spectra of all the compounds (recorded in nujol) exhibit

a single band in the region 24900-24300 an-’; this band may be assigned to a

charge transfer

(n-l)do, nsO of titanim and zirconium in all these complexes.

in accord with the electronic configuration

Attempts to prepare these compounds by reacting bis (7’-fluorenyl) - titaniumdichloride and bisC~5-fluorenyl)zirconi~dichloride with the

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5 Tablc I Characteristic infrared bands of (7 -C13H9)2M S2CNRR' C1

~

1 Sr . Compound Peak positions (cm- ) No.

(hl-CI) (M-S) (C-N) (C'=S) (C-H) (C-I+) (C-C) (C-H) stret- asp. in plane out of ching plane

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

385m

350111

380m

390m

385m

380m

382m

335m

350m

378m

37 Rm

380m

360m 1505s 9985

362m ISOOS 9955

358m 1510s 10005

356m 1510s 10005

360m 1505s 10005

362m 1500s 10005

365m 1510s 9935

360m 1510s 10005

360m 1505s 10005

348m 1510s 9955

350m 1510s 9965

358111 1505s 10005

3110m

3105m

3110m

3110m

3110m

3125m

3110m

3110m

3105111

3100m

3105111

3120111

1450m 10255

1440111 10305

1435m 10255

1440m 10305

1440m 10205

1450m 10255

1445m 10205

1445111 10205

1440m 10255

1430m 10155

1435111 10205

1440m 10205

810v5

820v5

310v5

815v5

810v5

eoovs

810v5

soovs

815v5

JlOVS

320v5

825v5

-__

m = medium; s = strong; vs = very strong

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TITANIUM (IV) AND ZIRCONIUM (IV) COMPOUNDS

sodium salt of an appropriate dithiocarbamate in solvents like THF or

benzene give impure products.

68 9

EXPERIMENTAL

MATERIALS

All the reagents used for the preparation of these compounds were of

analytical grade. Extra pure titanium tetrachloride (Riedel-de Haen) and

zirconium tetrachloride (E.Merck) were employed.

from Fluka and used as such without further purification. Nitrobenzene for

conductance measurements was purified by the method described by Fay et al.

Fluorene was obtained

18

METHODS Bis( ~5-fluorenyl)titanium[IV)dichloride and bis(7 5 -fluorenyl)-

zirconium(IV)dichloride were prepared by reacting titanium tetrachloride and

zirconium tetrachloride with fluorene, instead of sodium fluorenfde with

continuous stirring for 18-20 hours under dry nitrogen as described by

Samuel and Selton ,

conditions.

19 All operations were carried out under strictly anhydrous

The product formed was recrystallised from hot EtOH.

Sodium salt of the N,N-disubstituted dithiocarbamate ligand Na(S2CNRR')

(where R = alkyl, R' = phenyl or cyclohexyl) were prepared by the reaction

of equimolar amounts of the appropriate secondary amine, carbon disulphide

and sodium hydroxide in aqueous medium (10-15°C)20. Because the sodium salt

contain water of crystallisation, it was necessary to dry them in vacuo over

phosphorus pentoxide, first at room temperature and then at llO°C, until

their infrared spectra showed no water or only trace of water.

PREPARATION OF COMPLEXES

All the complexes were prepared in ir similar manner. Bis( 7'-fluorenyl)-

titanium(1V)dichloride and bis (~5-fluorenyl)zirconium(IV) dichloride (0.01

mle) were stirred in diwthoxyethamr ca. 50 el with aquimolar amounts of

anhydrous sodium N,N-disubstituted dithiocrrbamates for 16-20 hours under dry

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'Tablc 11. Analytical data of (7 5 -C13Hg)21M(S2CNRR')C1

. Compound Found (Calc.)% Sr . No. C H M S N C1

1. ( f-C13H9)2Ti(S2CN(CH3,C6H5)] C1

2. (T5-Cl3H9) 2Ti [S2CN(C21I5 ,C6HsfJ C1

3. (7 5 -C13119)2Ti[S2CN(i-C3H7,C61-15JJ C1

(y 5 -C13119)2Ti [S2CN(C2H5,C6IIll)] C1

4. ( I\5-C1311,)2Ti[S2CN(Cl13,C6Hll)J C1

5.

6. (75-C13H9)2Ti [S2CN(i-C3H7,C61111Y C1

7. ( ~5-C13tlg)2Zr~'2CN(CH3,C6115fJ Cl

6* (7 5 -C1311g)2ZrIs2CN(C2H5.CgH5)) c1

10. (7 5 -c~~II~)~z~~~cN(cI~~,c~II~~)Jc~

9. ( ~5-C1311s) ,Zr[S2CN(i-C3H, ,C6tls] C1

11. (~5-C1311,)2Zr[S2CN(C2H5,C61111)lC1

C13Hg)2Zr [S2CN(i-C3H7,C6H11)J C1

68.6 (68.53)

68.8 (68.92)

69.1 (69.30)

67.6 (67.34)

65.3 (68.25)

65.5 (68.64)

63.6 (63.88)

64.3 (64.36)

64.7 (64.79)

63.3 (63.28)

63.6 (63.76)

64.0 (64.221

4.3 (4.37)

4.4 (4.59)

4.8 (4.82)

5,3 (5.32)

5.4 (5.52)

5.6 (5.72)

4.0 (4.07)

4.2 (4.29)

4.4 (4.50)

4.9 (4.96)

5.1 (5.16)

5.2 (5.35)

8.0 (8.05)

7.8 (7.86)

7.5 (7.68)

7.8

7.8

(7.96)

(7.78)

7.5 (7.61)

14.1 (14.28)

13.8 (13.99)

13.5 (13.68)

14.1 (14.15)

13.7 (13.85) 13.4

(13.56)

10.5 (10.75)

10.4 (10.52)

10.2 (10,261

10.6 (10.64)

10.3 (10.40)

10.0 (10.12)

9.9 (10.02)

9.7 (9.81)

9.4 (9.60)

9.9 (9.93)

9.6 (9.71)

9.4 (9.51)

2.2 (2.35)

2.3 (2.30)

2.2 (2.25)

2.3 (2.33)

2.2 (2,271

2.2 (2.22)

2.1 (2.19)

2.1 (2.15)

2.0 (2.09)

2.1 (2.17)

2.0 (2.13)

2.0 (2.08)

6.0 (5.96)

5.8 (5.52)

5.6 (5.69)

5.8 (5.90)

5.6 (5.77)

5.7 (5.64)

5.4 (5.56)

5.3 (5.45)

5.4 (5.33)

5.6 (5.51)

5.2 (5.39)

5.2 (5.28)

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I 5 Table 111. Yield and physical characteristics of (7 -C H ) M S2CNRR C1 13 9 2

Sr . Compound No. Co 1 our Yield Dec. temp. Conductance

(%I (OC) Molari t y 3 x 10

Mol. Wt. Found (Calc. )

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

Yellow 72

Brown 70

Pale brown 70

Reddish brown 68

Brown 69

Light brown 70

Light brown 72

White 68

Yellowish 64 white

Brownish white 66

White 70

White 64

123-125

114-118

94-99

88-92

86-88

90-92

106-109

112-115

117-119

98-102

80-84

86-89

0.50 0.28

0.50 0.34

0.50 0.38

0.50 0.44

0.50 0.42

0.50 0.42

0.50 0.34

0.50 0.30

0.50 0.32

0.50 0.38

0.50 0.44

0.50 0.42

593.1(595.4)

607.2 (609.4)

622.0(623.4)

600.0 (601.4)

614.1(615,4)

628.2 (629.4)

636,8 (638.72)

650.5 (652.72)

665,4(666.72)

642.5(644.72)

656.0 (658.72)

670.2 (672.72)

2 -1 in ohm-' cm mole

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692 SHARMA AND KAUSHIK

nitrogen. The solution w a s then filtred and its volume was reduced to ca. 20 pl

Crystals of the products were obtained by adding excess of petroleum ether and

allowing mixture to stand overnight.

recrystallised from hot EtOH and dried over phosphorus pentmide (-v 2 hours),

These were filtered, washed with EtOH,

ANUYSBS

Titanium and zirconium were determined gravimetrically as Ti02 and Zr02

respectively and chlorine was detennined as silver chloride,

estbted by Kjeldahl's method.

the Messengers method, as described by VogelU.

and hydrogen contents of the complexes were carried out by the Microanalytical

Laboratories of the Department of Chmistry, University of Delhi, Delhi undial.

The analytical data of the complexes are given in

Nitrogen w a s

Sulphur in these compounds was estimated by

Microanalysis of carbon

Table 11.

PHYSICAL MeAsUREMENTs

Melting points were taken on a hot stage apparatus and are uncorrected,

Molecular weights were determined in benzene by a Gallenkanp ( U . K . ) Ebullio-

meter fitted with a thsrmister sensor.

Conductance measurements were carried out in nitrobenzene on a

Bechnann Couductivity Bridge model RC-18A). Table I11 lists the yield and

physical data of the complexes.

Infrared spectra were recorded in KBr pellets in the region 4000-200 an''

with a Perkin Elmerdtl Gratting Spectrophotometer. Electronic spectra of the

complexes were run on a Perkin Elmer 4000A instrument in the 400-750 nm range,

Magnetic measurement were made by GOUY'S method using CuSO,, as calibrant at

room temperature.

0

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TITANIUM (IV) AND ZIRCONIUM (IV) COMPOUNDS 693

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