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Studies on Some Substituted and Substituted Mixed Halomanganates(II) a

B. N. Thakur , R. S. Prasad

a c

a

, N. K. Jha & Elbashir E. Ali

b a

Department of Chemistry , Indian Institute of Technology , New Delhi, 110 016, India b

Department of Chemistry , Al-Fateh University , Tripoli, Libya c

Department of Chemistry , St. Columba's College , Hazaribag, 825301, India Published online: 06 Dec 2006.

To cite this article: B. N. Thakur , R. S. Prasad , N. K. Jha & Elbashir E. Ali (1988) Studies on Some Substituted and Substituted Mixed Halomanganates(II), Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 18:2, 197-214, DOI: 10.1080/00945718808060537 To link to this article: http://dx.doi.org/10.1080/00945718808060537

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SYNTH. REACT. INORG. MET.-ORG. CHEM., 18(2), 197-214 (1988)

STUDIES ON SOW SUBSTITUTED AND SUBSTITUTED MIXED HALOMANGANATES(11) Thakur, R.S. Prasad+ and M.K. Department of Chemistry, Indian I n s t i t u t e of Technology, New Delhi 110 016, India B.N.

*

Jha


-

and Elbashir E. A l i

Department of Chemistry, Al-Fateh University, Tripoli, Libya

ABSTRACT

Substituted and substituted mixed tetrahalornanganates(I1) of the type R[FanLX$ and R[MX2Y’I (where R = (C2Hg)4N, (n-C3%)4N, (n-C4Hg)4N, (C6H5)4P or (c6%)4kb; L = quinoline or triphenylphosphine, X and Y = C1, B r or I ) have been i s o l a t e d and characterized. From spectral and magnetic s t u d i e s , these complexes are found t o possess tetrahedrally coordinated M(11) ion. INTRODUCTION

I n recent years, there has been growing i n t e r e s t in the studies on halomanganates(I1) owing t o t h e i r phase t r a n s i t i o n a l , two-dimensional magnetic and 1 Although a number of l a t t i c e dynamical properties

.

+ Department of chdt- s k y , St. Columba’s College Hazaribag-825301, India.

197 Copyright 0 1988 by Marcel Dekker, Inc.

THAKUR ET AL.

198

,

simple halomanganates( 11) ( MKIX,+)~' (X = C1, B r o r I ) , are known2 there a r e only a few reports i n the literature on substituted halomanganates (11) , [IUhLX3](where L = substituted imidazoles and X and Y = C 1 , B r o r 1)3-6 and only one on substituted mixed halomanganates(II)? I n continuation of our work on halomanganates(11)~*9, we are reporting i n this communication the i s o l a t i o n and characterization of a few substituted and substituted mixed halomanganates(I1). Downloaded by [Tufts University] at 09:32 22 October 2014

,

RESULTS AND DISCUSSION

The complexes l i s t e d in Table I, were prepared by the interaction of manganese(I1) halide (prepared in s i t u f r o m manganese(I1) halide tewahydrate using 2,2 ' -dimethoxypropane) w i t h tetraalkylammoniurn/ tetraphenylphosphonium (or arsonium) halide and quinol i n e (or triphenylphosphine) i n 1:l:l molar r a t i o in a non-aqueous solvent. The equations f o r these react i o n s may be represented by:

--

The newly formed compounds are greenish yellow, c r y s t a l l i n e s o l i d s with sharp melting points. The fact t h a t repeated c r y s t a l l i s a t i o n from non-aqueous solvents, like a c e t a n i t r i l e or nitromethane, yields compounds of same composition and melting range indicates that these compounds are not physical

HALOMANGANATES(I1)

199

mixtures. These compounds are soluble i n nitromethane, nitrobenzene, ethanol, chloroform and insoluble i n benzene, carbontetrachloride and diethylether. Molar Conductance The values of the molar conductance (ohm” cm2 mol-I) of these complexes (Table I) a t loo3 M nitromethane solution ( a t 20 f 1.C) f a l l within the generally acceptable range f o r 1 :I e l e c t r o l y t e sI 0 confirming the presence of the ionic species manifest e d i n the molecular formula of these complexes.

-


,

Magnetic Moments The room temperature magnetic moment values corrected f o r diamagnetic corrections” (5.74-5.99 BM, Table I ) a r e i n the usual range reported f o r t e t r a hedral and pseudotetrahedral Mn(I1) complexes12

.

F a r I R Spectra

,

Substituted halomanganates(I1) ( W X 3 ) - (where L = triphenylphosphine or quinoline; X = C 1 or Br) may be assumed t o be derived from the simple tetrahalomanganates(II), ( M ~ I X ~ ) ~ . , which are known t o be

,

tetrahedral13, although the formal symmetry i n the present case i s reduced t o C On this basis the 3v’ degenerate vibrations in the case of (RcIX,,+)~- with nearly Td symmetry s p l i t and give rise t o s i x I R active ~ i b r a t i o n s ’ ~ out ; of these s i x vibrations three w i l l be stretching modes, two f o r the (luh-X), one f o r the (ivhn-L) ( i n f a c t , in the present case m-P or MI+ stretching mode) and the remaining three w i l l be the deformation modes. On the other hand, M&%Yspecies w i t h Cs symmetry would give r i s e t o nine vib-

Compound

96 Y i e l d Elements % Found 96 Calcd.

M.P.

("a 1

P'[MC13(Ph3P)3

2

65

4

4.26 13e25 6.76

m

c1

62.20

C

660 Og 4.79 13.62 7.27

m H

C

H Br

>

b

66,14 244-6 4.59 13.94 7.20 62.45 262 4.34 13.17 60 80

AM (ob-l cm2m01-1 ) 7

79

77

re (B.M 8

5.8 Downloaded by [Tufts University] at 09:32 22 October 2014

3 C H c1

45.20 5.1 5 34.62 7.82

m

-

5.8

45.45 268 02 5.09 (decamp. 1

5.7

34.88 7.99

58

P [MnC12Br(Ph3P)]

58

E [mC12Br(Ph3P)]

62.49 4.33 8.78

62.30 4.63 8.93 9.67 6. W

m

81

52.21 228-30 5.85 11.85 13.36 9-78

52.27 5.87 12.26 13.37 9-30

80

56.29 3.90 26.75 6.13

56.10 4.06 26.91 6.22

Br lyh

C H

c1 Br Mtl

C

H C1 Br

55

C H Br

I

.

278

250

78

9.B

60 80 45.61 186-8 5.44 20.23 16.06 6.95

76

5.8 Downloaded by [Tufts University] at 09:32 22 October 2014

45 85 5.41 20.31 16.28 7.1 1

m

5.9

TABLE I Con

TABLE I Contd. 1

A[WC121 (Ph3P)]

2

54

5

C H

4

18.12

I

51.40 .6.20 10.23

c1

rn 60

144-6

51.39 6.15 10.11

b

3

7.83

7.85

C H

48.41 6,71 13.60 15.33 10.54

218-20

230-2 (decomp.)

82-4

7

8

5.75

78 Downloaded by [Tufts University] at 09:32 22 October 2014

62,94 4.28 16.89 8.72

62.90 4.33 16.63 8.54

MI C H Br

c1

48.38 6.80 13.52 '1'5.37 10.41

79

18.10

41.35 5.73 39.30 9.01

41.45 5495 39-34 9.24

m

c1 62

63

C H

Br

m

81

83

A[MnBr21Q)

61

C H

c1 Br

m 59

58.79 4.00 10.51 11.85 8.15

48.21 6.73

C H

38.46 5.32 24.33 19.32 8.36

38.00 5.45 24.62 18.97 8.23

m

C

I

rn

21 6-8

138-40

78

86

82

82

5.

5.

5.


48.17 6.89 11.36

11.30

H Br

65

58.73 4.01 10.37 11.93 8.06

20.33 8.80

20.46 8.76

c1 I

Q = Quinoline.


204

THAKUR ET AL.

I I

m

I

In

m

N

0 N

9

cu

300s 290m 280m 277sh

A LmC121(Ph3P)]

281s 275m

P' [MnCl2Br(Ph3P))

220m 225s 21 8sh

A [MnC12BrQ)

3

-.

-

222s

185s

1 9 2 ~

192s

170111

175m 182mS

-

(

2 Downloaded by [Tufts University] at 09:32 22 October 2014

A @nBr21Q)

220vs 210sh

2


206

THAKUR ET AL.

r a t i m s l 4 , a l l of which are both I R and Raman active; out of these nine vibrations, four will be stretching modes; two Mn-XI one I*-Y and one MI-L ( i n f a c t h - P or Mn-N) and the remaining f i v e w i l l be deformation modes, A l l the deformation modes could not be observed a s the spectra could be recorded only t o 100 crn-’. Even those observed could not be assigned unambiguously since absorption due t o cations as w e l l a s due t o triphenylphosphine/quinoline overlap i n the low energy region of the spectra. Table I1 l i s t e the various f a r I R bands and their t e n t a t i v e assignments which a r e based on the comparison w i t h the reported m-X (X = C 1 , B r or I ) , M-N and Mn-P vibrations i n r e l a t e d MD( 11) compoupnds8s15021 and a l s o on the assignments of the far I R s p e c t r a l bands of simi1-s species formed by C O ( I I ) and ~ ~ Ni(II)23. I n these complexes the d(Fh-Cl) (273-300 cm”), the $(m-Br) (218-235 cm-’), the 3 (McI-I) (185-192 cm-I), the J (IJIn-P) (165-182 cm-’) and d (Mn-N) (195-205 cm-I) values a r e i n good agreement w i t h those of other species22s23. The s h i f t in 2)m-x in (X = C 1 t o Br) i s reported t o be 70-80 cm” while it i s 90-108 cm-’ i n case of X = C 1 t o I20,21 I n our case such c l e a r cut variation is not expected due t o varying stoichiometries of the complex anions. S h i f t s i n L’m-x (X = C 1 t o B r ) i s 50-55 cm” which is less than in simple tetrahaloman@;anates(II) w h i l e this shift f o r C1 t o I is 100-110 cm” which i s i n the same range a s in simple tetrahalomanganates(I1).

d4-

0

Electronic Spectra The observation t h a t these substituted and s u b s t i t u t e d mixed halomanganates(I1) have c o l o u r s varying f r o m yellowish-green t o greenish-yellow, i s indicative of the pres6nce


HALOMANGANATES(II) 207

I

I

mvenumber Ccm-'1

1

THAKUR ET A L .

208

24

.


of t e t r a h e d r a l :-h(II) i h these complexes Thus, on the b a s i s of t e t r a h e d r a l geometry one would expect n i n e s e x t e t q u a r t e t t r a n s i t i o n s from t h e 6A1 ground s t a t e t o the q u a r t e t e x c i t e d s t a t e s d e r i v e d from 4G, 4 D , 4F' and 4F l e v e l s .

The bands l i s t e d i n Table 111 a r e almost c o l q a r a b l e t o those r e p o r t e d f o r (ErCY2Y2) 2- (Y = C1, Sr clr I) and (?-bx4l2(X = CI, Br o r I) s p e c i e s8s25-27, except t h a t a fewer number of bands has been observed i n t h e p r e s e n t study. Thus, i n t h e range .y20750-24390 cm-' only one band is observed f o r most of t h e conplexes a s compared t o the 6 4 4 expected three bands correspondin t o the A1 4 TI ( GI, 6A1 + 4T2 ( 4 G ) and 6A1 + 4E, t A1 (4G) t r a n s i t i o n s .

TABLE 111. E l e c t r o n i c S p e c t r a l Data of Some of t h e Complexes

compound

Band P o s i t i o n (cm")

P * [?lC13(Ph3P)]

20747, 22124, 26738, 34722, 35088, 36232 21739, 26666, 34482, 35971, 37313

E [1.hCl2Br (Ph3P

>3

22222, 24390, 27027, 36496

21276, 32050, 33333, 34482, 37453 A [PTI-IB~~IQ]

'

B @nC121Q3

21276, 25641 , 32051, 33333 21276, 27027, 32051

209


HALOMANGANATES(II)

1

I

300

I

I

330 LOO Wavelength ( nm )

I

500

I n the middle energy region 425640-27030 cm” only one band could be observed f o r most of t h e coiplexes, which m y be assigned t o any one of t h e t h r e e t r a n s i t i o n s ‘4, --i) 4T2 (4D) ; 6Al 4 4E (4D), 6Al 4 4T1 (4P). S i m i l a r l y , i n the high energy region i.e. above 35000 cm-’ only one band could be observed for t h e majority of the complexes which may be assigned t o any of one of t h e t h e e t r a n s i t i o n s 6A 4A2 (4F), 6A, 44TI (4F) and

+

6A1 + 4T2 (4:). I n view o f the fewer number of bands observed i n the p r e s e n t case a q u a n t i t a t i v e a n a l y s i s of the s p e c t r a has n o t been c a r r i e d out.

210

THAKUR ET AL.


Thus, on the besis of the s p e c t r a l and magnetic s:ujies, i t c m be concluded that these compounds contain t e t r e h e d r a l l y coordinated mmgznese(I1) anion,the s t r u c t u r e of which i s suggested below:

EXPERIMTAL

Materials Manganese dichloride tetrahydrate (BDH, India), manganese bromide tetrahydrate, tetraethylammonium c N o r ide/br omide and t e tra-n-pr opylammmium iodide (BDH, England), tetraphenyl phosphonium chloride/ bromide and tetraphenylarsonium chloride (Fluka) and triphenyl phosphine (BDH, England) were used a s Quinoline (BDH, England) was used after received. d i s t i l l a t i o n under low pressure. Ethanol, nitromethane, a c e t o n i t r i l e and n-butanol were p u r i f i e d and d r i e d by standard methods28

.

Method of preparation A l l the s u b s t i t u t e d and s u b s t i t u t e d mixed t e t r a halomanganates(I1) were prepared by the following general method. 0.01 mol manganese(I1) halide tetrahydrate was refluxed with 2 m l of Z,Z'-dimethoxypropane i n an

HALOMANGANATES(IX)

211


.

absolute ethanol-n-butanol mixture (25 m l , 1 :1 v/v) To i t was added a hot solution of the appropriate tetraalkylammonium/tetraphenylphosphonium/tetraphenylarsonium halide (0.01 mol) and ligand (quinoline or triphenylphosphine (0.01 mol) i n the same mixed solvent (25 ml). The r e s u l t i n g solution was refluxed for about one hour and cooled inside a desiccator over fused CaC12. Yellowish green c r y s t a l s of varying shades were formed which were f i l t e r e d and r e c r y s t a l l i sed from acetonitrile. Thus, for example P' [MnC13(PPh3)] was prepared by refluxing 0,OI mol (1.98 g) of WCl2. 4H20 with 2 ml of 2,2'-dimethoxypropane i n absolute ethanol n-butanol mixture (25 ml, 1:l v/v>. To it was added a hot solution of 0.07 mol (4.19 g) tetraphenylphosphonium chloride and 0.01 mol (2.62 g) of triphenyl phosphine i n the same mixed solvent. The resulting solution was refluxed f o r one hour and allowed t o crystallise. Yellowish green c r y s t a l s were formed which were f i l t e r e d , and r e c r y s t a l l i s e d from ace t o n i t r i l e Analysis C and H were determined by microanalytical C 1 , B r and I methods by CDRI, Luchow, India. I%, were determined a s reported earlier899.

Physical Measurements Melting points were determined by using an electrothermal apparatus. Conductance measurements were carried out in M solution in nitromethane a t 20 + IOC on a WG PYE type conductance unit. Nagnetic s u s c e p t i b i l i t i e s were measured by Faraday's method. Far I R spectra were recorded in Nujol mulls i n the range 50-350 cm" on a Polytec FIR 30 a t RSIC,

-

-

THAKUR ET AL.

212

I I T Madras. A Unicam SP 700 spectrophotometer with a reflectance attachment was used t o record the d i f f u s e r e f l e ctance spectrum i n the range 2$0-1000 nm.

ACKNOWLEDGEMENT


B.N.T. and R.S.P. thank U.G.C., India f o r awarding a Teacher Fellowship and a N a t i o n a l Associateship, re spect ively.

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Received: Accepted:

27 August, 1986 11 December, 1987

Referee I : K. Moedritzer Referee 11: J. J . Alexander