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Intensity of ff bands of neodymium chloride alcohol solvates
Notes 4. P. S. Zacharias, B. Behera and A. Chakravorty, J. Am. Chem. Soc. 90, 7363 (1968). 5. E. Bamberger, Lie& Ann. 420, 137 (1919). 6. R. L. Dutta and S. Lahiry. J. Indian Chem. Soc. 40, 857 (1963). 7 C. F. Bell, Metal Chelation. p. 38 Claredon Press, Oxford {1077!.
1065
8. R. L. Dutta and R. Sharma, J. lnorg. NucL Chem. in press. 9. R. L. Dutta and S. P. Banerjee, J. Indian Chem. Soc. 51,497 (1974). 10. R. L. Dutta and A. Bhattacharya, J. lnorg. Nucl. Chem. in press.
/. imm,,, nucl (hem ~lq 4~, pp I06~-1(170 1981 Printed in Greal Britain
0022-19021811051065~6502.0010 Pergam(m Press Lid
Intensity of .f-f bands of neodymium c h l o r i d e alcohol solvates (Received 17 March 1980: received for publication 29 August 1980) Recent results revealed[I,2] that in alcohol solutions of lanthanide chlorides, at least in the case of Eu 3+ and Yb~+ ions, there exist mixed solvates, i.e. both chloride ions and solvent molecules are present in the Ln 3+ ion first coordination sphere. This conclusion was drawn from an analysis of the charge transfer transitions in the spectra of Eu 3÷ and Yb3+ chlorides in alcohols (methyl, ethyl, n-propyl), where two separate C.T. bands were observed and identified as C.T. transitions from the alcohol molecule and chloride ion to the Ln 3+ ion on the basis of the Je~rgensen's concept of electronegativity[3,4]. In our previous paper[I] we have reported that the energy of the first f - d transition in the Pr ~+ chloride alcohol solvates varied for different alcohols. These data also confirmed our suggestion that alcohol molecules are present in the first coordination sphere of the lanthanide ion. In the work reported here, we have tried to apply the intensity analysis method to the solution spectra of neodymium chloride dissolved in simple aliphatic alcohols like methanol, ethanol and n-propanol. We expect this method to be helpful in the determination of the structure of lanthanide alcohol solvates. The chosen system was relatively simple, especially in the case of anhydrous NdCI~ where the solvent was always present in great excess. For better explanation of the intensity analysis data it seemed interesting to calculate the nepheloauxetic effect because some authors still argue about the sources of hypersensitivity in lanthanide compound solution spectra considering the covalency parameter to be responsible for the intensity alterations f5].
EXPERIMENTAL Reagents. Anhydrous NdC13 was prepared from the Nd203 (99,99~, Koch-Light) by the Freeman and Smith method[6], by the chlorination and dehydratation of hydrated chloride using SOC12 vapour. Anhydrous chlorides were checked for the t~resence of -OH stretching vibrations in the IR region 06003500cm ~). The product was considered anhydrous when no -OH vibrations were observed in the NdCI3 (suspended in Nujol) IR spectrum. Hydrated neodymium chloride was recrystallized from an aqueous HC1 solution. CH3OH, C2HsOH, n-C3H70H were dried by heating with CaO, then with metallic magnesium and finally distilled off. The product was rectified on a column (72 theoretical plates). Such alcohols contain no more than l0 4% of H20[7]. The absorption spectra measurements were performed on a Cary 14 spectrophotometer. Appropriate alcohols were used as standard solutions. The concentrations of neodymium chloride were about 10 2 M. The areas of the f - f bands were calculated numerically by the graphical integration method and expressed in terms of oscillator strengths. P : 432 × 10`9 f~" t(o')do" where e is the molar extinction coefficient for the particular value and cr is the wave number in [cm q.
The wave numbers of the selected f - f transitions and the appropriate oscillator strengths for anhydrous and hydrated NdCI3 alcohol solutions are listed in Tables 1-3. The experimental oscillator strengths values were used for the calculation of Judd parameters according to the equation[8]: P = ~_, ~,~(/N%llu'~qlf~%,)z/(2J+
l)
A
where U ~A~are the matrix elements of the unit tensor operator calculated by Carnall et a/.[8] in the intermediate coupfing scheme, fN*jfmxF r are the initial and final states of electronic transition and J is the total quantum number. For the best assignments of particular electronic levels, the calculations were performed for the different sets of levels :and the results with minimal mean square errors were considered:
[E(AP)2] '/z S= t / ~ 3 J where i is the number of available equations and Ap is the difference between experimental oscillator strength value and calculated oscillator strength value for fitted r, parameters. It has to be pointed out, that calculations were done for two different sets of Nd 3+ levels: (a) omitting the group of transitions to the states 4D1/2, 2111/2, 4Dm and 4D3/2 with the wave numbers in the range 26300-29,600 cm-~, (b) including this set of levels. The second set gave better agreement with Carnall et al.[8] for aquoion spectra with respect to the z4 and z6 values. In both cases however, the results clearly show that the trend in the variation of the r2 parameter values was well established, and could not be due to a more or less accurate fitting procedure.
RESULTSANDDISCUSSION The absorption spectra of PrCI3 and NdCI3 in alcohols gave evidence of different intensity distributions of f - f transitions and small shifts of the bands towards lower wave numbers in comparison with the positions of the aquoion bands. Nepheloauxetic parameters for all observed transitions of anhydrous and hydrated Pr 3÷ and Nd 3+ chlorides calculated by the Sinha method[9] are listed in Table 4
.~. sol /3 _
v. aq. n
where ~. sol is the wave number of solvate in [cm q, ~. aq. is the wave number of aqoion in [cm q, B is the nepheloauxetic effect parameter and n is the number of bands considered. The values of ¢1 are very close to 1 and are a valuable proof that the covalency in these systems does not change significantly in comparison with the aquoion. The intensity changes were described in terms of the Judd-Oefelt method. There was no point in performing such analysis for PrCI3, where the ap-
4F5/2
2H9/2
4F3/2
4F7/2
4G3/2
4F9/2
4Gsz 2
_- 5.60.10 -7
2.36
8.01
11820 - 10965 11510, 11447
7.31
12887 - 12048 12470, 12393
0.52
13908 - 12970 13563, 13510, 13344
15083 - 14184 14587
14.70
2.75
7.67
7.55
0.60
14.70
2G712
8.65 2.59
12870 - 12048' 12477, 12392 11834 - 11001 11515, 11455 = 5.74.10-7
8.40
0.53
16.28
6.63
2.00
0.53
10.61
2.34
8.17
8.98
0.68
16.35
5.74
1.37
0.61
10.97
Pexp. lO 6 Poal.106
13870m - 12937 13572, 13514, 13346
15038 - 14285 14611
17825 - 16475 17341, 17144, 17094
19505,19335,19055,18918
17794 - 16447 17318,17135,17079
5.89
19501,19324,19048,18911
4G7/2
4G9/2 5.90
22724 - 20530 21622, 21254, 20947
2KI~/2
1.42 20284 - 18553
1.69
20284 - 18519
22624 - 20534 4Gll/2 2D, 2"F3t~ 2G~/2 2K1~/2 21608, 21259, 20938
0.78
0.67
2D5/2 2P1/2 24036 -22724 23288, 23089
28670,28466,28050,27917
23474 22624 23277, 23095
9.95
9.59
28662,28457,28035,27956 -
29144 - 27174
~ [om-1]
29326 - 26667
Pexp.106 Poal.lO 6
4D1/2 2Ill/2 4D5/2 4D~/2
[om-I]
NdCl~.6H20
Table 1. The oscillator strength values of f-f transitions for anhydrous and hydrated NdCI3in methanol
Zo
6.44 6.93
2.11
13908 - 12937 13568, 13514,13351
12870 - 11976 12459, 12399
11820 - 10941 11494, 11429
4F7/2
4F5/2
4S3/2
2H9/2
S = 3.64.10 -7
18.82
17825 - 16447 17327,17123,17079
4G5/2
4G7/2
4F3/2
0.47
15083 - 14225 14599
4F9/2
5.74
1.50
9474,19331,19029,18939
18416
20284
4G7/2 -
21622,21245,20938
2K!5t2
22222 - 20492
2.44
6.76
6.58
18.83
0.53
5 •64
1.26
8.15 8.74 2.53
13889 - 12919 13559, 13514, 13355 12837 - 11990 12469, 12399 11834 - 11013 11504, 11442 S = 4.92.10 -7
20.78
0.56
17825 - 16447 17527, 17129, 17094
6.99
14992 - 14245 14609
1.74
19493,19342,19048,18921
20161 - 18416
21598, 21254, 20951
22727 - 20492
0.49
23810 - 22727 23283, 23095
0.60
23419 - 22727 23202, 23084 0.69
11.56
28653,28458,28043,27917
9.70
28612,28425,27988,27917
,Pexp. 106
29585 - 26385
~ [ o m -1]
NdCI~.6H20
26596 - 29326 9.92
Pexp -I06 Peal.t06
2x1~/2
2G9/2 4G9/2
4Gli/2 2D,2F3/2
4D1/2 2Ill/2 4D~/2 4D~/2 2D5/2 2P1/2
[om -I]
NdCI 3
Table 2. The oscillator strength values of [-/transitions for anhydrous and hydrated NdCI3in ethanol
2.48
8.20
8.72
20.84
0.67
6.22
1.41
0.66
11.85
Poa1-106
z O
2P1/2
2D5/2
4G7/2
4G5/2
4G9/2
2G~/2
4F5/2
2H9/2
4F3/2
4F7/2
4S3/2
4~9/2
2K1~/2
2K1~/2
2G~/2
4Gll/2 2D,2P3/2
2111/2
4D)/2
4D1/2
4D5/2
6.91 2.09
12854 - 11990 12461, 12399
11779 - 10941 11492, 11434
S = 5.33.10 -7
6.36
0.44
13889 - 12937 13550, 13486, 13358
15038 - 14286 14588
2.59
6.85
6.48
0.53
S = 4.81.10 -7
11779 - 10941 11507, 11448
12837 - 12062 12475, 12392
i13559~ 13495, 13351
13889 - 12919
15038 - 14286 14611
17857 - 16447 17341, 17138, 17094
17.99
17762 - 16420 17320, 17123, 17065 18.O2
!19501,19342,19055,18929
5.76
6.14
21622, 21254, 20951
19474,19350,19029,18911
1.30 20243 - 18518
1.43
22727 - 20408
20243 - 18215
21566, 21236, 20929
22573 - 20534
23923 - 22831 23294, 23089
0.45
23419 - 22831 23428, 23277, 23079 0.73
29155 - 27248 28670,28466,28050,27933
9.67
9.34
~ [om-l~
29412 - 26596
Pex~.lO61Poal.106
2.57
8.31
8.02
0.53
19.05
6.75
1.57
0.45
10.83
2.34
7.92
8.51
0.65
19.11
5.89
1.35
0.62
11.14
Pexp.106 Poal.106
NdCI~.6H20
28653,28433,28011,27894
~[om -1 ]
NdCl~
Table 3. The oscillator strength values of f-f transitions for anhydrous and hydrated NdCI3 in methanol n-propanol
Z o
1069
Notes Table 4. The nepheloauxetic B parameters for alcohol solvates of Pr 3+ and Nd 3+
CH~0H
n-C~HvOH
C2H50H
P
P PrCI~
0.994
0.995
0.994
PrCI~-6H20
0.994
0.995
0.994
NdCl~
0.995
0.995
0.994
NdCl)'6H20
0.995
0.995
0.995
Table 5. The % parameters of NdCI3 and NdCI3 aq. in alcohol solutions
T2.10 9
24 .I09
"~6 .I09
NdCI3-6H20
a
3.56 ~ 0.48
9.17 + 0.72
8.93 + 0.35
in CH)OH
b
5.13 ~ 0.42
6.58 + 0.39
9.60 + 0.65
NdCI3.6H20
a
6.24 Z 0.49
9.25 + 0.79
8.76 _+ 0 3 5
in C2H~OH
b
7.49 ~ 0.36
7.19 + 0.33
9.31 + 0.46
NaCI3-6H20
a
5.40 ~ 0.39
8.93 + 0.58
8.54 + 0.28
in n-C~H70H
'b
6.74 ~ 0.35
6.73 + 0.33
9.11 _+ 0 . 4 5
NdCI 3
a
3.05 ~ 0.43
8.57_+ 0 . 6 5
7.90_+ 0.31
in CH~OH
b
4.62 2 0.41
5.98 + 0.38
8.57 ! 0.'52
NdC13
a
6.17 ~ 0.33
7.66 + 0.50
6.84 + O.24
in C2H}OH
b
7.12 ~ 0.27
6.07+ 0.25
7.25 + 0.34
NdCI 3
a
5.35 ~ 0.48
8.23 + 0.72
6.72 + 0.35
in n-C~HTOH
b
6.76 ~ 0.35
5.89 _+ 0.36
7.33 + 0.49
1.20 ~ 0.41
6.44 + 0 . 3 6
I0.20+ 0.54
Nd+3 ( a q u o i o n ) [8]
- This result remains in agreement with that given by Sinha H4] a) 4,, 2T 4,, 4-. " 1 / 2 ' "11/2' " 5 / 2 ' "°3/2 states ommited b) The above states taken into account plication of the simplified Judd formula was rather doubtful[10]. The results of the intensity analysis for anhydrous and hydrated neodymium chlorides are given in Table 5. The data lead us to conclude that for both the NdC13-ROH and NdCIs.6H20-ROH systems with the different alcohols, the r2 parameters are the same within the limits of the Judd-Oefelt method error. This means that, in agreement with our previous results, the symmetry of the species formed was the same. It has to be pointed out that for different alcohols these values changed in the order: C2H~OH > n-CsHTOH > CHsOH > H20. The lowest 22 parameter value was observed for the neodymium chloride-methanol system, so a relatively small symmetry lowering could be expected. If the assumed Csh or D3h aquoion structure is correct[11], C3o symmetry for the species predominant in the methanol solution should be expected. For the NdCl3--ethanol system we observed significantly higher r2 parameters. According to Judd[12], all symmetries of C, and C,v type are equivalent from the hypersensitivity point of view. In our previous investigations we observed that for lanthanide complexes of lower symmetry the r,, parameter values could be distinguished even *Author to whom correspondence should be addressed.
within the C~,, symmetry group[13]. Such behaviour of the intensities could be explained by the partial participation of an inhomogenous dielectric mechanism in [-[ transitions. Thus C2~ symmetry can be assumed for the ethanol solvates. The same could be expected for the propanol. These conclusions are strongly supported by the fact that the charge-transfer analysis of the Eu s+ alcohol solvates has allowed us to determine tlheir composition as LnCls(CH3OH)6 and [LnCI2(C2HsOH)7]+ 1151. Institute of Chemist~ Unit~ersity of Wroclaw Wroclaw Poland
K. BUKIETYIqSKA B. JEZOWSKI-TRZEBIATOWSKA* B. KELLER REFERENCES
I. K. Bukietyflska, B. Keller and J. Legendziewicz, Proc. XlIlrd ICCC II, 373 (1970). 2. B. Keller, K. Bukietyhska and B. Jezowska-Trzebiatowska, Bull. Acad. Polon. Sci. ser. scL chim. XXIV(9), 763 (1976). 3. C. K. Jelrgensen, Molec. Phys. 2, 305 (1959); ibid. 5, 271 (1%2). ~,. J. L. Ryan and C. K. Jeirgensen, J. Phys. Chem. 70, 2845 (1%6). 5. D. E. Henrie, R. L. Fellows and G. R. Choppin, Coord. Chem. Rev. lg, 199 (1976).
1070
Notes
6. J. H. Freeman and M. L. Smith, J. lnorg. Nucl. Chem. 7, 224 (1958). 7. A. Weisberger and E. S. Proskauer, Organic Solvents Physical Properties and Methods of Purification. New York (1955). 8. W. T. Carnall, P. R. Fields and K. Rajnak, J. Chem. Phys. 49, 4412, 4424, 4443, 4447 and 4450 (1%7). 9. S. P. Sinha, Spectrochim. Acta 22, 57 (1%6).
10. R. D. Peacock, Structure and Bonding 22, 84 (1975). 11. R. Sarup and M. H. Crozier, J. Chem. Phys. 42, 371 (1%5). 12. B. R. Judd, J. Chem. Phys. 44, 839 (1966). 13. J. Legendziewicz, K. Bukietyhska and B. Je~towska-Trzebiatowska, Acta Phys. Acad. Sci. Hung. 35, 167 (1974). 14. S. P. Sinha, P. C. Metha and S. S. L. Surama, Molec. Phys. 23, 807 (1972). 15. B. Keller, unpublished.
0022-1902/81/051070-0250100/0 PergamonPressLtd.
Z inorg..ucl. Chem. Vol. 43, pp. 1070-1071, 1981 Printed in Great Britain
Synthesis of some new gallium and indium complexes with some sulphur containing iigands (Received 31 July 1979; received for publication 29 August 1980) The condensation of a-amino-fl-thiols with carbonyl compounds results in the formation of thiazolidines[1,2]. The presence of metal ions brings about a quantitative rearrangement of the cyclic structure to the Schiff base chelate analogous[3]. The present paper reports our results on the reactions of gallium and indium alkoxides with the following type of sulphur containing ligands: (1) Acetylacetone-2-mercaptoanil (H2ASP), CttH,3ONS, colourless crystalline solid, m.p. 85°C. (2) Salicylaldehyde-2-mercaptoanil(H2SSP), C,3HtIONS, yellow crystals, m.p. 134°C. (3) 2-Hydrooxyacetopbenone-2-mqcaptoanil (H2A'SP),Ct4HI3ONS,yellow shiny crystals, m.p. 99°C. (4) 2-Hydroxy naphthaldehyde-2-mercaptoanil, (H2NSP), C17HI3ONS, deep yellow solid, m.p. 145°C. EXPERIMENTAL All the techniques and chemicals used during the present investigations have been reported earlier[4-8]. The ligands were synthesized by the condensation of carbonyl compounds with 2aminobenzenethiol in absolute alcohol and recrystallized before use [2, 9-10]. Synthesis o[ metal complexes M(OPr% (where M = Ga(III) or In(III) and the ligand were mixed in dry benzene in appropriate ratio and refluxed for-25 hr. Rest of the preparation is as reported earlier[4-6]. Elemental analyses for the resulting
(OPri)M (ONS) and M2(ONS)3 type of compounds agreed with the theoretical values within the limits of experimental errors. The labile nature of the isopropoxy group of the (priO)M(ONS) complexes was shown by their exchange reactions with t-butanol and the resulting t-butoxy products have been isolated and analyzed. Physical measurements. Molecular weights were determined in refluxing benzene using a semi-microebulliometer(Gallen Kamp) using thermistor sensing. The electronic spectra were recorded on a Toshniwal Spectrophotometer with I cm quartz cells in the range of 600-200nm in chloroform and the IR spectra on a Perkin-Elmer-557 Grating IR Spectrophotometer in the range 4000-200cm-t. tHNMR spectra were recorded on a PerkinElmer R-12-B spectrometer as solutions in CDCl3 (TMS as tile internal standard). RESULTSAND DISCUSSION The spectral studies of the (PriO)M(SNO) and M2(SNO)3 products clearly indicate that a rearrangement of the heterocyclic ring takes place and finally metal Schiff base type derivatives are obtained. The products are coloured solids, stable up t o - 250°C and are soluble in most common organic solvents (except the complexes of H2SSP). The monoisopropoxy complexes are susceptible to hydrolysis and are dimeric in boiling benzene. The isopropoxy group may act as a bridge between the two metal atoms [7, 8], in which case the metal atoms appear to exist in an unusual penta-coordinate state [4, I I].
Table 1. IH NMR data for the ligand and the corresponding metal complexes in 8 (ppm) \ S. N 0.
C ~pound
~
N-H
c. 2
cH 3
5.0
3.20
2.30, 1.95
-
2.50, 2.30,
1.
H2ASP
7.0
2.
Ga(ASP)(OPr i)
7.1
~0 M-c.~(i~op,.opoxy) 0 H
5.6
&.2
1.80, 1.45 3.
GR2(ASP) 3
7.1
-
2.50, 2.30, 1./40
5.6
-
4.
In(ASP)(OPr i)
7.3
-
2.45, 2.25,
5.6
4.2
1.80, 1.35 5.
In2(ASP) 3
7.3
-
2.50, 2.30 1.35
5.6
1065
8. R. L. Dutta and R. Sharma, J. lnorg. NucL Chem. in press. 9. R. L. Dutta and S. P. Banerjee, J. Indian Chem. Soc. 51,497 (1974). 10. R. L. Dutta and A. Bhattacharya, J. lnorg. Nucl. Chem. in press.
/. imm,,, nucl (hem ~lq 4~, pp I06~-1(170 1981 Printed in Greal Britain
0022-19021811051065~6502.0010 Pergam(m Press Lid
Intensity of .f-f bands of neodymium c h l o r i d e alcohol solvates (Received 17 March 1980: received for publication 29 August 1980) Recent results revealed[I,2] that in alcohol solutions of lanthanide chlorides, at least in the case of Eu 3+ and Yb~+ ions, there exist mixed solvates, i.e. both chloride ions and solvent molecules are present in the Ln 3+ ion first coordination sphere. This conclusion was drawn from an analysis of the charge transfer transitions in the spectra of Eu 3÷ and Yb3+ chlorides in alcohols (methyl, ethyl, n-propyl), where two separate C.T. bands were observed and identified as C.T. transitions from the alcohol molecule and chloride ion to the Ln 3+ ion on the basis of the Je~rgensen's concept of electronegativity[3,4]. In our previous paper[I] we have reported that the energy of the first f - d transition in the Pr ~+ chloride alcohol solvates varied for different alcohols. These data also confirmed our suggestion that alcohol molecules are present in the first coordination sphere of the lanthanide ion. In the work reported here, we have tried to apply the intensity analysis method to the solution spectra of neodymium chloride dissolved in simple aliphatic alcohols like methanol, ethanol and n-propanol. We expect this method to be helpful in the determination of the structure of lanthanide alcohol solvates. The chosen system was relatively simple, especially in the case of anhydrous NdCI~ where the solvent was always present in great excess. For better explanation of the intensity analysis data it seemed interesting to calculate the nepheloauxetic effect because some authors still argue about the sources of hypersensitivity in lanthanide compound solution spectra considering the covalency parameter to be responsible for the intensity alterations f5].
EXPERIMENTAL Reagents. Anhydrous NdC13 was prepared from the Nd203 (99,99~, Koch-Light) by the Freeman and Smith method[6], by the chlorination and dehydratation of hydrated chloride using SOC12 vapour. Anhydrous chlorides were checked for the t~resence of -OH stretching vibrations in the IR region 06003500cm ~). The product was considered anhydrous when no -OH vibrations were observed in the NdCI3 (suspended in Nujol) IR spectrum. Hydrated neodymium chloride was recrystallized from an aqueous HC1 solution. CH3OH, C2HsOH, n-C3H70H were dried by heating with CaO, then with metallic magnesium and finally distilled off. The product was rectified on a column (72 theoretical plates). Such alcohols contain no more than l0 4% of H20[7]. The absorption spectra measurements were performed on a Cary 14 spectrophotometer. Appropriate alcohols were used as standard solutions. The concentrations of neodymium chloride were about 10 2 M. The areas of the f - f bands were calculated numerically by the graphical integration method and expressed in terms of oscillator strengths. P : 432 × 10`9 f~" t(o')do" where e is the molar extinction coefficient for the particular value and cr is the wave number in [cm q.
The wave numbers of the selected f - f transitions and the appropriate oscillator strengths for anhydrous and hydrated NdCI3 alcohol solutions are listed in Tables 1-3. The experimental oscillator strengths values were used for the calculation of Judd parameters according to the equation[8]: P = ~_, ~,~(/N%llu'~qlf~%,)z/(2J+
l)
A
where U ~A~are the matrix elements of the unit tensor operator calculated by Carnall et a/.[8] in the intermediate coupfing scheme, fN*jfmxF r are the initial and final states of electronic transition and J is the total quantum number. For the best assignments of particular electronic levels, the calculations were performed for the different sets of levels :and the results with minimal mean square errors were considered:
[E(AP)2] '/z S= t / ~ 3 J where i is the number of available equations and Ap is the difference between experimental oscillator strength value and calculated oscillator strength value for fitted r, parameters. It has to be pointed out, that calculations were done for two different sets of Nd 3+ levels: (a) omitting the group of transitions to the states 4D1/2, 2111/2, 4Dm and 4D3/2 with the wave numbers in the range 26300-29,600 cm-~, (b) including this set of levels. The second set gave better agreement with Carnall et al.[8] for aquoion spectra with respect to the z4 and z6 values. In both cases however, the results clearly show that the trend in the variation of the r2 parameter values was well established, and could not be due to a more or less accurate fitting procedure.
RESULTSANDDISCUSSION The absorption spectra of PrCI3 and NdCI3 in alcohols gave evidence of different intensity distributions of f - f transitions and small shifts of the bands towards lower wave numbers in comparison with the positions of the aquoion bands. Nepheloauxetic parameters for all observed transitions of anhydrous and hydrated Pr 3÷ and Nd 3+ chlorides calculated by the Sinha method[9] are listed in Table 4
.~. sol /3 _
v. aq. n
where ~. sol is the wave number of solvate in [cm q, ~. aq. is the wave number of aqoion in [cm q, B is the nepheloauxetic effect parameter and n is the number of bands considered. The values of ¢1 are very close to 1 and are a valuable proof that the covalency in these systems does not change significantly in comparison with the aquoion. The intensity changes were described in terms of the Judd-Oefelt method. There was no point in performing such analysis for PrCI3, where the ap-
4F5/2
2H9/2
4F3/2
4F7/2
4G3/2
4F9/2
4Gsz 2
_- 5.60.10 -7
2.36
8.01
11820 - 10965 11510, 11447
7.31
12887 - 12048 12470, 12393
0.52
13908 - 12970 13563, 13510, 13344
15083 - 14184 14587
14.70
2.75
7.67
7.55
0.60
14.70
2G712
8.65 2.59
12870 - 12048' 12477, 12392 11834 - 11001 11515, 11455 = 5.74.10-7
8.40
0.53
16.28
6.63
2.00
0.53
10.61
2.34
8.17
8.98
0.68
16.35
5.74
1.37
0.61
10.97
Pexp. lO 6 Poal.106
13870m - 12937 13572, 13514, 13346
15038 - 14285 14611
17825 - 16475 17341, 17144, 17094
19505,19335,19055,18918
17794 - 16447 17318,17135,17079
5.89
19501,19324,19048,18911
4G7/2
4G9/2 5.90
22724 - 20530 21622, 21254, 20947
2KI~/2
1.42 20284 - 18553
1.69
20284 - 18519
22624 - 20534 4Gll/2 2D, 2"F3t~ 2G~/2 2K1~/2 21608, 21259, 20938
0.78
0.67
2D5/2 2P1/2 24036 -22724 23288, 23089
28670,28466,28050,27917
23474 22624 23277, 23095
9.95
9.59
28662,28457,28035,27956 -
29144 - 27174
~ [om-1]
29326 - 26667
Pexp.106 Poal.lO 6
4D1/2 2Ill/2 4D5/2 4D~/2
[om-I]
NdCl~.6H20
Table 1. The oscillator strength values of f-f transitions for anhydrous and hydrated NdCI3in methanol
Zo
6.44 6.93
2.11
13908 - 12937 13568, 13514,13351
12870 - 11976 12459, 12399
11820 - 10941 11494, 11429
4F7/2
4F5/2
4S3/2
2H9/2
S = 3.64.10 -7
18.82
17825 - 16447 17327,17123,17079
4G5/2
4G7/2
4F3/2
0.47
15083 - 14225 14599
4F9/2
5.74
1.50
9474,19331,19029,18939
18416
20284
4G7/2 -
21622,21245,20938
2K!5t2
22222 - 20492
2.44
6.76
6.58
18.83
0.53
5 •64
1.26
8.15 8.74 2.53
13889 - 12919 13559, 13514, 13355 12837 - 11990 12469, 12399 11834 - 11013 11504, 11442 S = 4.92.10 -7
20.78
0.56
17825 - 16447 17527, 17129, 17094
6.99
14992 - 14245 14609
1.74
19493,19342,19048,18921
20161 - 18416
21598, 21254, 20951
22727 - 20492
0.49
23810 - 22727 23283, 23095
0.60
23419 - 22727 23202, 23084 0.69
11.56
28653,28458,28043,27917
9.70
28612,28425,27988,27917
,Pexp. 106
29585 - 26385
~ [ o m -1]
NdCI~.6H20
26596 - 29326 9.92
Pexp -I06 Peal.t06
2x1~/2
2G9/2 4G9/2
4Gli/2 2D,2F3/2
4D1/2 2Ill/2 4D~/2 4D~/2 2D5/2 2P1/2
[om -I]
NdCI 3
Table 2. The oscillator strength values of [-/transitions for anhydrous and hydrated NdCI3in ethanol
2.48
8.20
8.72
20.84
0.67
6.22
1.41
0.66
11.85
Poa1-106
z O
2P1/2
2D5/2
4G7/2
4G5/2
4G9/2
2G~/2
4F5/2
2H9/2
4F3/2
4F7/2
4S3/2
4~9/2
2K1~/2
2K1~/2
2G~/2
4Gll/2 2D,2P3/2
2111/2
4D)/2
4D1/2
4D5/2
6.91 2.09
12854 - 11990 12461, 12399
11779 - 10941 11492, 11434
S = 5.33.10 -7
6.36
0.44
13889 - 12937 13550, 13486, 13358
15038 - 14286 14588
2.59
6.85
6.48
0.53
S = 4.81.10 -7
11779 - 10941 11507, 11448
12837 - 12062 12475, 12392
i13559~ 13495, 13351
13889 - 12919
15038 - 14286 14611
17857 - 16447 17341, 17138, 17094
17.99
17762 - 16420 17320, 17123, 17065 18.O2
!19501,19342,19055,18929
5.76
6.14
21622, 21254, 20951
19474,19350,19029,18911
1.30 20243 - 18518
1.43
22727 - 20408
20243 - 18215
21566, 21236, 20929
22573 - 20534
23923 - 22831 23294, 23089
0.45
23419 - 22831 23428, 23277, 23079 0.73
29155 - 27248 28670,28466,28050,27933
9.67
9.34
~ [om-l~
29412 - 26596
Pex~.lO61Poal.106
2.57
8.31
8.02
0.53
19.05
6.75
1.57
0.45
10.83
2.34
7.92
8.51
0.65
19.11
5.89
1.35
0.62
11.14
Pexp.106 Poal.106
NdCI~.6H20
28653,28433,28011,27894
~[om -1 ]
NdCl~
Table 3. The oscillator strength values of f-f transitions for anhydrous and hydrated NdCI3 in methanol n-propanol
Z o
1069
Notes Table 4. The nepheloauxetic B parameters for alcohol solvates of Pr 3+ and Nd 3+
CH~0H
n-C~HvOH
C2H50H
P
P PrCI~
0.994
0.995
0.994
PrCI~-6H20
0.994
0.995
0.994
NdCl~
0.995
0.995
0.994
NdCl)'6H20
0.995
0.995
0.995
Table 5. The % parameters of NdCI3 and NdCI3 aq. in alcohol solutions
T2.10 9
24 .I09
"~6 .I09
NdCI3-6H20
a
3.56 ~ 0.48
9.17 + 0.72
8.93 + 0.35
in CH)OH
b
5.13 ~ 0.42
6.58 + 0.39
9.60 + 0.65
NdCI3.6H20
a
6.24 Z 0.49
9.25 + 0.79
8.76 _+ 0 3 5
in C2H~OH
b
7.49 ~ 0.36
7.19 + 0.33
9.31 + 0.46
NaCI3-6H20
a
5.40 ~ 0.39
8.93 + 0.58
8.54 + 0.28
in n-C~H70H
'b
6.74 ~ 0.35
6.73 + 0.33
9.11 _+ 0 . 4 5
NdCI 3
a
3.05 ~ 0.43
8.57_+ 0 . 6 5
7.90_+ 0.31
in CH~OH
b
4.62 2 0.41
5.98 + 0.38
8.57 ! 0.'52
NdC13
a
6.17 ~ 0.33
7.66 + 0.50
6.84 + O.24
in C2H}OH
b
7.12 ~ 0.27
6.07+ 0.25
7.25 + 0.34
NdCI 3
a
5.35 ~ 0.48
8.23 + 0.72
6.72 + 0.35
in n-C~HTOH
b
6.76 ~ 0.35
5.89 _+ 0.36
7.33 + 0.49
1.20 ~ 0.41
6.44 + 0 . 3 6
I0.20+ 0.54
Nd+3 ( a q u o i o n ) [8]
- This result remains in agreement with that given by Sinha H4] a) 4,, 2T 4,, 4-. " 1 / 2 ' "11/2' " 5 / 2 ' "°3/2 states ommited b) The above states taken into account plication of the simplified Judd formula was rather doubtful[10]. The results of the intensity analysis for anhydrous and hydrated neodymium chlorides are given in Table 5. The data lead us to conclude that for both the NdC13-ROH and NdCIs.6H20-ROH systems with the different alcohols, the r2 parameters are the same within the limits of the Judd-Oefelt method error. This means that, in agreement with our previous results, the symmetry of the species formed was the same. It has to be pointed out that for different alcohols these values changed in the order: C2H~OH > n-CsHTOH > CHsOH > H20. The lowest 22 parameter value was observed for the neodymium chloride-methanol system, so a relatively small symmetry lowering could be expected. If the assumed Csh or D3h aquoion structure is correct[11], C3o symmetry for the species predominant in the methanol solution should be expected. For the NdCl3--ethanol system we observed significantly higher r2 parameters. According to Judd[12], all symmetries of C, and C,v type are equivalent from the hypersensitivity point of view. In our previous investigations we observed that for lanthanide complexes of lower symmetry the r,, parameter values could be distinguished even *Author to whom correspondence should be addressed.
within the C~,, symmetry group[13]. Such behaviour of the intensities could be explained by the partial participation of an inhomogenous dielectric mechanism in [-[ transitions. Thus C2~ symmetry can be assumed for the ethanol solvates. The same could be expected for the propanol. These conclusions are strongly supported by the fact that the charge-transfer analysis of the Eu s+ alcohol solvates has allowed us to determine tlheir composition as LnCls(CH3OH)6 and [LnCI2(C2HsOH)7]+ 1151. Institute of Chemist~ Unit~ersity of Wroclaw Wroclaw Poland
K. BUKIETYIqSKA B. JEZOWSKI-TRZEBIATOWSKA* B. KELLER REFERENCES
I. K. Bukietyflska, B. Keller and J. Legendziewicz, Proc. XlIlrd ICCC II, 373 (1970). 2. B. Keller, K. Bukietyhska and B. Jezowska-Trzebiatowska, Bull. Acad. Polon. Sci. ser. scL chim. XXIV(9), 763 (1976). 3. C. K. Jelrgensen, Molec. Phys. 2, 305 (1959); ibid. 5, 271 (1%2). ~,. J. L. Ryan and C. K. Jeirgensen, J. Phys. Chem. 70, 2845 (1%6). 5. D. E. Henrie, R. L. Fellows and G. R. Choppin, Coord. Chem. Rev. lg, 199 (1976).
1070
Notes
6. J. H. Freeman and M. L. Smith, J. lnorg. Nucl. Chem. 7, 224 (1958). 7. A. Weisberger and E. S. Proskauer, Organic Solvents Physical Properties and Methods of Purification. New York (1955). 8. W. T. Carnall, P. R. Fields and K. Rajnak, J. Chem. Phys. 49, 4412, 4424, 4443, 4447 and 4450 (1%7). 9. S. P. Sinha, Spectrochim. Acta 22, 57 (1%6).
10. R. D. Peacock, Structure and Bonding 22, 84 (1975). 11. R. Sarup and M. H. Crozier, J. Chem. Phys. 42, 371 (1%5). 12. B. R. Judd, J. Chem. Phys. 44, 839 (1966). 13. J. Legendziewicz, K. Bukietyhska and B. Je~towska-Trzebiatowska, Acta Phys. Acad. Sci. Hung. 35, 167 (1974). 14. S. P. Sinha, P. C. Metha and S. S. L. Surama, Molec. Phys. 23, 807 (1972). 15. B. Keller, unpublished.
0022-1902/81/051070-0250100/0 PergamonPressLtd.
Z inorg..ucl. Chem. Vol. 43, pp. 1070-1071, 1981 Printed in Great Britain
Synthesis of some new gallium and indium complexes with some sulphur containing iigands (Received 31 July 1979; received for publication 29 August 1980) The condensation of a-amino-fl-thiols with carbonyl compounds results in the formation of thiazolidines[1,2]. The presence of metal ions brings about a quantitative rearrangement of the cyclic structure to the Schiff base chelate analogous[3]. The present paper reports our results on the reactions of gallium and indium alkoxides with the following type of sulphur containing ligands: (1) Acetylacetone-2-mercaptoanil (H2ASP), CttH,3ONS, colourless crystalline solid, m.p. 85°C. (2) Salicylaldehyde-2-mercaptoanil(H2SSP), C,3HtIONS, yellow crystals, m.p. 134°C. (3) 2-Hydrooxyacetopbenone-2-mqcaptoanil (H2A'SP),Ct4HI3ONS,yellow shiny crystals, m.p. 99°C. (4) 2-Hydroxy naphthaldehyde-2-mercaptoanil, (H2NSP), C17HI3ONS, deep yellow solid, m.p. 145°C. EXPERIMENTAL All the techniques and chemicals used during the present investigations have been reported earlier[4-8]. The ligands were synthesized by the condensation of carbonyl compounds with 2aminobenzenethiol in absolute alcohol and recrystallized before use [2, 9-10]. Synthesis o[ metal complexes M(OPr% (where M = Ga(III) or In(III) and the ligand were mixed in dry benzene in appropriate ratio and refluxed for-25 hr. Rest of the preparation is as reported earlier[4-6]. Elemental analyses for the resulting
(OPri)M (ONS) and M2(ONS)3 type of compounds agreed with the theoretical values within the limits of experimental errors. The labile nature of the isopropoxy group of the (priO)M(ONS) complexes was shown by their exchange reactions with t-butanol and the resulting t-butoxy products have been isolated and analyzed. Physical measurements. Molecular weights were determined in refluxing benzene using a semi-microebulliometer(Gallen Kamp) using thermistor sensing. The electronic spectra were recorded on a Toshniwal Spectrophotometer with I cm quartz cells in the range of 600-200nm in chloroform and the IR spectra on a Perkin-Elmer-557 Grating IR Spectrophotometer in the range 4000-200cm-t. tHNMR spectra were recorded on a PerkinElmer R-12-B spectrometer as solutions in CDCl3 (TMS as tile internal standard). RESULTSAND DISCUSSION The spectral studies of the (PriO)M(SNO) and M2(SNO)3 products clearly indicate that a rearrangement of the heterocyclic ring takes place and finally metal Schiff base type derivatives are obtained. The products are coloured solids, stable up t o - 250°C and are soluble in most common organic solvents (except the complexes of H2SSP). The monoisopropoxy complexes are susceptible to hydrolysis and are dimeric in boiling benzene. The isopropoxy group may act as a bridge between the two metal atoms [7, 8], in which case the metal atoms appear to exist in an unusual penta-coordinate state [4, I I].
Table 1. IH NMR data for the ligand and the corresponding metal complexes in 8 (ppm) \ S. N 0.
C ~pound
~
N-H
c. 2
cH 3
5.0
3.20
2.30, 1.95
-
2.50, 2.30,
1.
H2ASP
7.0
2.
Ga(ASP)(OPr i)
7.1
~0 M-c.~(i~op,.opoxy) 0 H
5.6
&.2
1.80, 1.45 3.
GR2(ASP) 3
7.1
-
2.50, 2.30, 1./40
5.6
-
4.
In(ASP)(OPr i)
7.3
-
2.45, 2.25,
5.6
4.2
1.80, 1.35 5.
In2(ASP) 3
7.3
-
2.50, 2.30 1.35
5.6