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Disulfoxide complexes with lanthanum perchlorate
J. inorg, nucl. Chem. Vol. 42, pp. 395-397 © Pergamon Press Ltd., 1980. Printed in Great Britain
0022-190218010301--0395/$02.00/0
DISULFOXIDE COMPLEXES WITH LANTHANUM PERCHLORATE ARDEN P. ZIPP and SYBIL G. ZIPP Chemistry Department, State University College, Cortland, NY 13045,U.S.A. (Received 31 January 1979, received.for publication 5 July 1979) Abstract--The synthesis and characterization of the complexes between La(CIO4)3and eleven disulfoxides with the formula RS(O) (CH2)xS(O)R are reported. In all cases, the lanthanum ion is eight-coordinated and bonded to the sulfoxide moieties via the oxygen atom. INTRODUCTION There have been a number of recent reports of complex formation between lanthanide compounds and suifoxidecontaining ligands, including dialkyl[1-7], diaryl[5, 8] and alicyclic [9-17] species. Until the present time, however, multidentate sulfoxide ligands have not been studied. (The potentially bidentate 1,4 dithiane 1,4 dioxide appears to utilize only one sulfoxide moiety in its complexes with the lanthanides[10--14].) As part of a continuing investigation of the behavior of bidentate sulfoxides and the influence of structural changes on this behavior, we have prepared and characterized a series of complexes between Ln(CIO4)3 and the ligands RS(O) (CH2)xS(O)R (where R = CH3 x = 2,3,4 and x = 2 R = C2H5, C3H7 and C(CH3)3), the results of which are reported here.
Preparation o.f complexes. Complexes were prepared by reacting an ethanolic solution (10ml) of the appropriate ligand (0.004mole) with an ethanolic solution of Ln(CIO4)3 '0.6H20 (0.001 mole) to which 5 ml of triethylorthoformate had been added as a dehydrating agent[24]. Crystalline products were formed either immediately or upon standing overnight. These were washed with ethanol and ether and dried over P20~ in vacuo. Analyses and IR measurements. All compounds were analyzed for lanthanum titrimetrically using EDTA with Eriochrome Black T as indicator[25] and for perchlorate gravimetrically using nitron[26]. Carbon and hydrogen analyses were carded out by Strauss Microanalytical Laboratories (Oxford, England). IR spectra were recorded for all ligands and complexes (as Nujol mulls between CsBr plates) from 300 to 4000cm -~ on a Beckman IR-12 spectrophotometer. RESULTS AND DISCUSSION One of the original reasons for undertaking this investigation was to determine whether the coordination number of eight normally found for La(III) would be affected by changes in either the nature of the terminal R group or the number of CH2 groups separating the suifoxide moieties (X). Such a change in stoichiometry is well-documented for La(III) complexes with monosulfoxides which exhibit a range of coordination numbers C . N . = 5 for 1,4 dithiane dioxide[10], 6 for dibutyl-[2] sulfoxide, 7.5 for tetramethylenesulfoxide[9] and 8 for dimethylsulfoxide[1] and even further variation with different anions. For example, the number of DMSO molecules coordinated changes from 8 when the counter ion is perchlorate to 7.4 when bexafluorophosphate is present[4] and to 4 when the nitrate ion is used (due to coordination of NO3-)[2, 3]. A change in stoichiometry from La(DP)2 (NO3)3 to La2(DP)3 (NO3)6, is also observed when the number of methylene groups separating the
EXPERIMENTAL Materials. Lanthanum perchlorate (G. F. Smith) and standard laboratory chemicals were used as received. Disulfoxides were obtained by oxidizing the parent dithianes with H202 in glacial acetic acid[18]. The solid disulfoxides were obtained by steam distilling the acetic acid and evaporating the water. These solids (which contain the d, 1 and meso isomers) were recrystallized repeatedly from acetonitrile to separate the low-melting more soluble isomer from the higher-melting less soluble one. The melting points cited below (uncorrected) provide an indication of the purity of the two isomers obtained by this procedure: 1,2 Bis(methylsulfinyl)ethane (MSE) 128-130°, 161-163°; 1,3 Bis(methylsulfinyl)propane (MSP 91-94°, 112-1130; 1,4 Bis(methyisulfinyl)butane (MSB) 80--82°, 118-120°; 1,2 Bis(ethylsulfinyl)ethane (ESE) 124--125°, 139-140°; 1,2 Bis(n-propylsulfinyl)ethane (PSE) 115-117°, 158-159"; 1,2 Bis(t-butylsulfinyl)ethane (BSE) 124-125°, 145-1470. In addition, all compounds were characterized by IR and NMR spectra and by titrations in acetic anhydride [19], which gave results suggesting a high degree of purity. ~P---O functions in tetraalkyi diphosphonates (DP) is Although assignments of configuration (meso or d, 1) have been made for the high and low melting fractions of a number of changed from 2 to 4[27]. Further, several of the didisulfoxides by means of NMR spectra, in the absence[20, 21] sulfoxides studied here have been found to produce and presence[22] of NMR shift reagents as well as by chemical complexes with differing coordination numbers when characterization and chromatographic separation[23], this has reacted with Cu(II). Specifically, the coordination numbeen most successful for species in which the sulfoxide groups "oer for Cu(II) changes from 6 (3 disulfoxides/CuII) to 4 are separated by a single methylene group. In these cases the two (2 disulfoxides]CuII) when the disulfoxide is changed hydrogen atoms in the meso isomers are in different environ- from MSE[28] to ESE (larger R) or to MSP or MSB ments and thus give rise to separate signals whereas the hydrogens in the d, 1 racemates are identical. For those sul- (greater X value)[29]. Although this change may be due foxides with x > 1, the unique character of the hydrogens of the in part to the tendency of copper to undergo tetragonal meso form is lost and the assignment of configuration can not be distortion[30], this behavior seemed to offer further made automatically. This problem is still under investigation, but reason to expect La(III) disulfoxide complexes to exhibit for the purposes of the present study, the compounds will be variations in stoichiometry. Thus, it was quite surprising identified in terms of their melting points alone. to obtain the results in Table 1 which clearly indicate a 395
396
A. P. ZIPP and S. G. ZIPP Table 1. Analyticaldata for LaL4 (CIO4h L
% La
% C
% H
% CIO4
12.71 (13.19)
18.50 (18.25)
4.65 (3.83)
29.10 (28.34)
13.26 (13.19)
16.72 (18.25)
5.02 (3.83)
29.09 (28.34)
MSP-high
12.43 (12.52)
21.25 (21.64)
4.90 (4.32)
27.15 (26.91)
MSB-high
11.98 (11.92)
23.67 (24.72)
5.30 (4.81)
26.36 (25.62)
12.16 (11.92)
24.12 (24.72)
5.57 (4.81)
24.99 (25.62)
11.83 (11.92
24.55 (24.72)
5.18 (4.81)
25.96 (25.62)
11.72 (11.92)
24.09 (24.72)
5.12 (4.81)
25.32 (25.62)
11.06 (10.88)
29.92 (30.06
5.93 (5.64)
23.06 (23.37)
10.84 (10.88)
30.37 (30.06)
5.70 (5.64)
23.49 (23.37)
10.27 (12.29)
33.63 (34.59)
6.27 (6.39)
21.77 (21.48)
10.21 (10.29)
33.76 (34.59)
8.39 (6.39)
22.16 (21.48)
MSE-high -low
-low
ESE-high -low
PSE-high -low
BSE-high -10W
ligand: metal ratio of 4:1 (implying a coordination number of 8 for La) regardless of the structure of the disulfoxide. The difference between the behavior of the disulfoxides reported here and that of monosulfoxides can be attributed to the greater complexing ability of the bidentate species [28] as well as the decreased impact of steric interferences when the two R groups are attached to different sulfoxide moieties. Similarly, the contrast between the behavior of disulfoxides and diphosphonates can be ascribed to the greater donor strength of the S=O group (relative to that of -~/P=O)
as
reflected in extraction studies of U(VI) [31], Th(IV)[32] and Ce(III)[33]. The greater donor strength would make
the sulfoxide complexes less susceptible to subtle changes in the ligand geometry and lead to the more consistent stoichiometry. In addition to establishing the stoichiometries of the compounds prepared, it was of interest to determine the mode of bonding adopted by the ambidentate sulfoxide group toward the La(III) ion. Thus, the IR spectra of the disulfoxides and the metal complexes were recorded. The major feature of interest in the former is the strong band near 1000 cm -j, which has been assigned to the S-O stretching frequency[34]. It is noteworthy that in the mull spectra of several of the disulfoxides this band is split (Table 2) suggesting that in the solid the sulfoxide groups are in different environments. The spectra of the lanthanum complexes differ from those of the ligands in
Table 2. IR spectral results for LaL4(CIOD3 ~ S O ( c m -I) (li~and)
~ S O (cm -I )
(complex)
1018
i000
1018
I000
MSP-hiqh
1045, 995
1002
MSB-high
1026
1000
1030
i000
1045, 1018
i001
1045, 1018
995
1015
990
1012
986
MSE-high -10W
-lOW
ESE-high -10W
PSE-high -lOW
BSE-high -low
1035, 1020
990
1032, 1018
991
Disulfoxide Complexes with lanthanum perchlorate the position of the S--O stretch (see below) and in the appearance of two new bands near ll00cm -~ and 620 cm -~ respectively. These have been assigned to the antisymmetric stretching and bending vibrations of the perchlorate ion[35]. The absence of splitting in the band at 1100 cm -~ provides evidence that the perchlorate ion is not coordinated[36] and, therefore, that the La(III) ion remains eight-coordinate in all of these species. The shift in the position of the sulfoxide absorbance to lower frequencies relative to its position in the free ligand has been shown[37] to be diagnostic to oxygen bonding by the sulfoxide moiety. (In contrast, sulfur bonding is indicated by a shift of vso to higher frequencies.) The fact that only a single sulfoxide stretching frequency is observed for each complex, despite the IR behavior of the pure ligand, provides support for the view that all the sulfoxides are equivalent in a given complex. The oxygen-bonding between La(III) and these disulfoxides is consistent with the behavior of this ion toward other sulfoxides[l-17] as well as that of other hard[38] metal ions toward sulfoxides and the fact that no difference in behavior is observed for the high and low melting forms of the various disulfoxides is also consistent with a previous study of the complexes of his(phenylsulfinyl)methane and ethane [39]. In summary, the complexes between La(CIO4)3 and disulfoxides are eight-coordinate and oxygen-bonded as shown by elemental analyses and IR spectroscopy. REFERENCES
1. V. N. Krishnamurthy and S. Soundararajan, J. lnorg. Nucl. Chem. 29, 517 (1967). 2. S. K. Ramalingam and S. Soundararajan, J. Inorg. Nucl. Chem. 29, 1763 (1967). 3. K. Kfishma Bhandary, H. Manohar and K. V. Venkatesan, J. Inorg. Nucl. Chem. 37, 1997 (1975). 4. M. Kawashita Kuya, O. A. Serra, V. K. Lakatos Osorio, J. Inorg. Nucl. Chem. 37, 1998 (1975). 5. D. K. Kappikar and S. Soundararajan, J. Inorg. Nucl. Chem. 38, 174 (1976). 6. J. R. Behrendt and S. K. Madan, J. lnorg. Nucl. Chem. 38, 1827 (1970. 7. V. K. Lakatos Osorio and A. M. Passos Felecissimo, lnorg. Chim Acta 19, 245 (1976). 8. S. K. Ramalingam and S. Soundararajan, Bull. Chem. Soc. Japan 41,106 (1968). 9. P. D. Bertan and S. K. Madan, J. lnorg. Nucl. Chem. 34, 3081 (1972). 10. R. Najjan and G. Vicentini, lnorg. Nucl. Chem. Lett. 9, 577 (1973).
JINC Vol. 42, No. 3--F
397
11. G. Vicentini and L. C. Garla, J. lnorg. Nucl. Chem. 35, 3973 (1973). 12. G. Vicentini and M. Pettier, J. Inorg. Nucl. Chem. 35, 3973 (1973). 13. G. Vicentini, L. B. Zinner and L. R. F. de Carvalho, J. Inorg. Nucl. Chem. 37, 607 (1975). 14. G. Vicentini, L. B. Zinner and L. R. F. de Carvalho, J. Inorg. Nucl. Chem. 37, 2021 (1975). 15. A. M. P. Felicissimo,G. Vicentiniand L. B. Zinner,J. Inorg. Nucl. Chem. 39, 1935 (1977). 16. L. B. Zinner and G. Vicentini,J. Inorg.Nucl. Chem. 39, 1835 (1977). 17. G. Vicentini, L. B. Zinner and K. Zinner, J. lnorg. Nucl. Chem. 40, 690 (1978). 18. E. V. Bell and G. M. Bennett, J. Chem. Soc. 1798 (1927). 19. S. Siggia, Quantitative Organic Analysis via Functional Groups, p. 621, 3rd Edn. Wiley New York, (1963). 20. R. Louw and H. Nieuwenhuyse, Chem. Commun. 1561, (1968). 21. M. Cinquini, S. Colonna and F. Taddei, Boll. Sci. Fac. Chim. Ind. Bologna 27, 231 (1969). 22. J. L. Greene and P. B. Shelvlin, Chem. Commun. 1092 (1971). 23. M. Cinquini and S. Colonna, Int. J. Sulfur Chem. 8, 603 (1976). 24. P. W. N. M. Van Leeuwen and W. L. Groeneveld, Inorg. Nucl. Chem. Lett.3, 145 (1967). 25. S. J. Lyle and M. M. Rahman, Talanta 10, 1177 (1963). 26. F.J. Welcher, Organic AnalyticalReagents.D. Van Nostrand, New York (1959). 27. W. E. Stewart and T. H. Siddall,J. Inorg. Nucl. Chem. 33, 2965 (1971). 28. S. K. Madan, C. M. Hull and L. J. Herman, Inorg. Chem. 7, 491 (1968). 29. A. P, Zipp and S. K. Madan, Inorg.Chim. Acta 22, 49 (1977). 30. J. E. Huheey, InorganicChemistry,Principleso/Structureand Recativity,2nd Edn., p. 374 et seq. Harper & Row, New York (1978). 31. S. R. Mohanty and A. S. Reedy, J. [norg.Nucl. Chem. 37, 1791
(1975). 32. S. R. Mohanty and A. S. Reddy, J. Inorg. Nucl. Chem. 37, 1977 (1975). 33. A. S. Reddy and L. K. Reddy, J. Inorg.Nucl. Chem. 39, 1683
(1977). 34. M. Avram and G. D. Mateescu, IR Spectroscopy, pp. 292-295. Wiley-Interscience, New York (1972). 35. B. J. Hathaway and A. E. Underhill, J. Chem. Soc. 3091 (1961). 36. S. F. Parkovic and D. W. Meek, Inorg. Chem. 4, 109 (1965). 37. F. A. Cotton and R. Francis, J. Am. Chem. Soc. g2, 2986 (1960); M. J. Bennett, F. A. Cotton and D. L. Weaver, Nature, 212, 286 (1966). 38. R. G. Pearson, J. Chem. Ed. 45, 581,643 (1968). 39. T. R. Musgrave and G. D. Kent, J. Coord. Chem. 2, 23 (1972).
0022-190218010301--0395/$02.00/0
DISULFOXIDE COMPLEXES WITH LANTHANUM PERCHLORATE ARDEN P. ZIPP and SYBIL G. ZIPP Chemistry Department, State University College, Cortland, NY 13045,U.S.A. (Received 31 January 1979, received.for publication 5 July 1979) Abstract--The synthesis and characterization of the complexes between La(CIO4)3and eleven disulfoxides with the formula RS(O) (CH2)xS(O)R are reported. In all cases, the lanthanum ion is eight-coordinated and bonded to the sulfoxide moieties via the oxygen atom. INTRODUCTION There have been a number of recent reports of complex formation between lanthanide compounds and suifoxidecontaining ligands, including dialkyl[1-7], diaryl[5, 8] and alicyclic [9-17] species. Until the present time, however, multidentate sulfoxide ligands have not been studied. (The potentially bidentate 1,4 dithiane 1,4 dioxide appears to utilize only one sulfoxide moiety in its complexes with the lanthanides[10--14].) As part of a continuing investigation of the behavior of bidentate sulfoxides and the influence of structural changes on this behavior, we have prepared and characterized a series of complexes between Ln(CIO4)3 and the ligands RS(O) (CH2)xS(O)R (where R = CH3 x = 2,3,4 and x = 2 R = C2H5, C3H7 and C(CH3)3), the results of which are reported here.
Preparation o.f complexes. Complexes were prepared by reacting an ethanolic solution (10ml) of the appropriate ligand (0.004mole) with an ethanolic solution of Ln(CIO4)3 '0.6H20 (0.001 mole) to which 5 ml of triethylorthoformate had been added as a dehydrating agent[24]. Crystalline products were formed either immediately or upon standing overnight. These were washed with ethanol and ether and dried over P20~ in vacuo. Analyses and IR measurements. All compounds were analyzed for lanthanum titrimetrically using EDTA with Eriochrome Black T as indicator[25] and for perchlorate gravimetrically using nitron[26]. Carbon and hydrogen analyses were carded out by Strauss Microanalytical Laboratories (Oxford, England). IR spectra were recorded for all ligands and complexes (as Nujol mulls between CsBr plates) from 300 to 4000cm -~ on a Beckman IR-12 spectrophotometer. RESULTS AND DISCUSSION One of the original reasons for undertaking this investigation was to determine whether the coordination number of eight normally found for La(III) would be affected by changes in either the nature of the terminal R group or the number of CH2 groups separating the suifoxide moieties (X). Such a change in stoichiometry is well-documented for La(III) complexes with monosulfoxides which exhibit a range of coordination numbers C . N . = 5 for 1,4 dithiane dioxide[10], 6 for dibutyl-[2] sulfoxide, 7.5 for tetramethylenesulfoxide[9] and 8 for dimethylsulfoxide[1] and even further variation with different anions. For example, the number of DMSO molecules coordinated changes from 8 when the counter ion is perchlorate to 7.4 when bexafluorophosphate is present[4] and to 4 when the nitrate ion is used (due to coordination of NO3-)[2, 3]. A change in stoichiometry from La(DP)2 (NO3)3 to La2(DP)3 (NO3)6, is also observed when the number of methylene groups separating the
EXPERIMENTAL Materials. Lanthanum perchlorate (G. F. Smith) and standard laboratory chemicals were used as received. Disulfoxides were obtained by oxidizing the parent dithianes with H202 in glacial acetic acid[18]. The solid disulfoxides were obtained by steam distilling the acetic acid and evaporating the water. These solids (which contain the d, 1 and meso isomers) were recrystallized repeatedly from acetonitrile to separate the low-melting more soluble isomer from the higher-melting less soluble one. The melting points cited below (uncorrected) provide an indication of the purity of the two isomers obtained by this procedure: 1,2 Bis(methylsulfinyl)ethane (MSE) 128-130°, 161-163°; 1,3 Bis(methylsulfinyl)propane (MSP 91-94°, 112-1130; 1,4 Bis(methyisulfinyl)butane (MSB) 80--82°, 118-120°; 1,2 Bis(ethylsulfinyl)ethane (ESE) 124--125°, 139-140°; 1,2 Bis(n-propylsulfinyl)ethane (PSE) 115-117°, 158-159"; 1,2 Bis(t-butylsulfinyl)ethane (BSE) 124-125°, 145-1470. In addition, all compounds were characterized by IR and NMR spectra and by titrations in acetic anhydride [19], which gave results suggesting a high degree of purity. ~P---O functions in tetraalkyi diphosphonates (DP) is Although assignments of configuration (meso or d, 1) have been made for the high and low melting fractions of a number of changed from 2 to 4[27]. Further, several of the didisulfoxides by means of NMR spectra, in the absence[20, 21] sulfoxides studied here have been found to produce and presence[22] of NMR shift reagents as well as by chemical complexes with differing coordination numbers when characterization and chromatographic separation[23], this has reacted with Cu(II). Specifically, the coordination numbeen most successful for species in which the sulfoxide groups "oer for Cu(II) changes from 6 (3 disulfoxides/CuII) to 4 are separated by a single methylene group. In these cases the two (2 disulfoxides]CuII) when the disulfoxide is changed hydrogen atoms in the meso isomers are in different environ- from MSE[28] to ESE (larger R) or to MSP or MSB ments and thus give rise to separate signals whereas the hydrogens in the d, 1 racemates are identical. For those sul- (greater X value)[29]. Although this change may be due foxides with x > 1, the unique character of the hydrogens of the in part to the tendency of copper to undergo tetragonal meso form is lost and the assignment of configuration can not be distortion[30], this behavior seemed to offer further made automatically. This problem is still under investigation, but reason to expect La(III) disulfoxide complexes to exhibit for the purposes of the present study, the compounds will be variations in stoichiometry. Thus, it was quite surprising identified in terms of their melting points alone. to obtain the results in Table 1 which clearly indicate a 395
396
A. P. ZIPP and S. G. ZIPP Table 1. Analyticaldata for LaL4 (CIO4h L
% La
% C
% H
% CIO4
12.71 (13.19)
18.50 (18.25)
4.65 (3.83)
29.10 (28.34)
13.26 (13.19)
16.72 (18.25)
5.02 (3.83)
29.09 (28.34)
MSP-high
12.43 (12.52)
21.25 (21.64)
4.90 (4.32)
27.15 (26.91)
MSB-high
11.98 (11.92)
23.67 (24.72)
5.30 (4.81)
26.36 (25.62)
12.16 (11.92)
24.12 (24.72)
5.57 (4.81)
24.99 (25.62)
11.83 (11.92
24.55 (24.72)
5.18 (4.81)
25.96 (25.62)
11.72 (11.92)
24.09 (24.72)
5.12 (4.81)
25.32 (25.62)
11.06 (10.88)
29.92 (30.06
5.93 (5.64)
23.06 (23.37)
10.84 (10.88)
30.37 (30.06)
5.70 (5.64)
23.49 (23.37)
10.27 (12.29)
33.63 (34.59)
6.27 (6.39)
21.77 (21.48)
10.21 (10.29)
33.76 (34.59)
8.39 (6.39)
22.16 (21.48)
MSE-high -low
-low
ESE-high -low
PSE-high -low
BSE-high -10W
ligand: metal ratio of 4:1 (implying a coordination number of 8 for La) regardless of the structure of the disulfoxide. The difference between the behavior of the disulfoxides reported here and that of monosulfoxides can be attributed to the greater complexing ability of the bidentate species [28] as well as the decreased impact of steric interferences when the two R groups are attached to different sulfoxide moieties. Similarly, the contrast between the behavior of disulfoxides and diphosphonates can be ascribed to the greater donor strength of the S=O group (relative to that of -~/P=O)
as
reflected in extraction studies of U(VI) [31], Th(IV)[32] and Ce(III)[33]. The greater donor strength would make
the sulfoxide complexes less susceptible to subtle changes in the ligand geometry and lead to the more consistent stoichiometry. In addition to establishing the stoichiometries of the compounds prepared, it was of interest to determine the mode of bonding adopted by the ambidentate sulfoxide group toward the La(III) ion. Thus, the IR spectra of the disulfoxides and the metal complexes were recorded. The major feature of interest in the former is the strong band near 1000 cm -j, which has been assigned to the S-O stretching frequency[34]. It is noteworthy that in the mull spectra of several of the disulfoxides this band is split (Table 2) suggesting that in the solid the sulfoxide groups are in different environments. The spectra of the lanthanum complexes differ from those of the ligands in
Table 2. IR spectral results for LaL4(CIOD3 ~ S O ( c m -I) (li~and)
~ S O (cm -I )
(complex)
1018
i000
1018
I000
MSP-hiqh
1045, 995
1002
MSB-high
1026
1000
1030
i000
1045, 1018
i001
1045, 1018
995
1015
990
1012
986
MSE-high -10W
-lOW
ESE-high -10W
PSE-high -lOW
BSE-high -low
1035, 1020
990
1032, 1018
991
Disulfoxide Complexes with lanthanum perchlorate the position of the S--O stretch (see below) and in the appearance of two new bands near ll00cm -~ and 620 cm -~ respectively. These have been assigned to the antisymmetric stretching and bending vibrations of the perchlorate ion[35]. The absence of splitting in the band at 1100 cm -~ provides evidence that the perchlorate ion is not coordinated[36] and, therefore, that the La(III) ion remains eight-coordinate in all of these species. The shift in the position of the sulfoxide absorbance to lower frequencies relative to its position in the free ligand has been shown[37] to be diagnostic to oxygen bonding by the sulfoxide moiety. (In contrast, sulfur bonding is indicated by a shift of vso to higher frequencies.) The fact that only a single sulfoxide stretching frequency is observed for each complex, despite the IR behavior of the pure ligand, provides support for the view that all the sulfoxides are equivalent in a given complex. The oxygen-bonding between La(III) and these disulfoxides is consistent with the behavior of this ion toward other sulfoxides[l-17] as well as that of other hard[38] metal ions toward sulfoxides and the fact that no difference in behavior is observed for the high and low melting forms of the various disulfoxides is also consistent with a previous study of the complexes of his(phenylsulfinyl)methane and ethane [39]. In summary, the complexes between La(CIO4)3 and disulfoxides are eight-coordinate and oxygen-bonded as shown by elemental analyses and IR spectroscopy. REFERENCES
1. V. N. Krishnamurthy and S. Soundararajan, J. lnorg. Nucl. Chem. 29, 517 (1967). 2. S. K. Ramalingam and S. Soundararajan, J. Inorg. Nucl. Chem. 29, 1763 (1967). 3. K. Kfishma Bhandary, H. Manohar and K. V. Venkatesan, J. Inorg. Nucl. Chem. 37, 1997 (1975). 4. M. Kawashita Kuya, O. A. Serra, V. K. Lakatos Osorio, J. Inorg. Nucl. Chem. 37, 1998 (1975). 5. D. K. Kappikar and S. Soundararajan, J. Inorg. Nucl. Chem. 38, 174 (1976). 6. J. R. Behrendt and S. K. Madan, J. lnorg. Nucl. Chem. 38, 1827 (1970. 7. V. K. Lakatos Osorio and A. M. Passos Felecissimo, lnorg. Chim Acta 19, 245 (1976). 8. S. K. Ramalingam and S. Soundararajan, Bull. Chem. Soc. Japan 41,106 (1968). 9. P. D. Bertan and S. K. Madan, J. lnorg. Nucl. Chem. 34, 3081 (1972). 10. R. Najjan and G. Vicentini, lnorg. Nucl. Chem. Lett. 9, 577 (1973).
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