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Complexes of lanthanum(III), neodymium(III) and samarium(III) chloride with 1,2-ethylenebisdiphenylphosphine and arsine oxides
Notes 8. A. K. Majumdar and R. G. Bhattacharyya, Jr. inorg. nucl. Chem., 35, 4296 (1973). 9. A. K. Majumdar and R. G. Bhattacharyya, J. Indian chem. Soc., 50, 701 (1973).
581
10. R. G. Bhattacharyya and D. C. Bera, Indian J. Chem. (in press). 11. R. S. Drago, D. W. Meek, M. D. Joesten and L. L. Roche, Inorg. Chem., 2, 124 (1963).
.1. inorg, nucl. Chem.. 1975,Vol. 37. p. 581. PergamonPress. Printedin Great Britain
Complexes of lanthanum(III), neodymium(III) and samarium(III) chloride with 1,2-ethylenebisdiphenylphosphine and arsine oxides (Received 2 February 1974) COMPLEXES of lanthanide(III) chlorides with a number of monotertiaryphosphine oxides[I-4] and triphenylarsine oxide[I,2] have been reported. In continuation of our previous work[5] the complexes of lanthanum(III), neodymium(III) and samarium(III) chlorides with 1,2ethylenebisdiphenylphosphine oxide (EPO) and arsine oxide (EAO) have been isolated. These complexes have been characterized with the help of elemental analysis, i.r. spectra and magnetic susceptibility data.
EXPERIMENTAL The ligands were prepared by the methods already reported in literature [6, 7]. The complexes were prepared by mixing the warm solutions of anhydrous lanthanide(III) chlorides and the ligands in 1:2 molar ratio in butanol. Carbon, hydrogen and phosphorus content of the complexes was estimated by Australian Microanalytical Service, Melbourne. Chloride was estimated by Volhard method. I.R. spectra of the complexes were recorded in nujol on i.r. 20 Beckman i.r. spectrophotometer. The magnetic susceptibility of the complexes was measured by Gouy method. RESULTS AND DISCUSSION The elemental analysis of the complexes indicate that all but one complexe correspond to the general empirical formula Ln2CI~L3-xH20 (where Ln is La(III), Nd(III) or Sm(III); L is EPO or EAO and x is 0-2). With EPO, however, neodymium(III) chloride yields NdC13. EPO,H20. The i.r. spectra of all the complexes of lanthanidc(III) chlorides with EPO record three bands near 1165, 1145 and 1085cm -~ as compared to one at ll80cm ~ in the free ligand. This splitting and downward shift in the phosphoryl stretch indicates coordination through phosphoryl oxygen. The band near 1165 and 1145 cm ~may be assigned to the coordinated but non-bridging phosphoryl group whereas the band near 1085 cm ' may be assigned to the bridging phosphoryl stretch. In the i.r. spectra of the complexes of lanthanide(III) chlorides with EAO three absorption bands are observed around 920, 880 and 850cm ~. These bands may be assigned to the coordinated arsenyl group. Since in the complexes of lanthanide(III) salts with triphenylarsine
oxide[l,2] and tribenzylarsine oxide[8] no absorption band is observed near 850 cm ~, this band may be assigned to bridging arsenyl group. The splitting in this stretch along with an upward shift has, however, been reported by other workers also[l, 2, 8]. The values of magnetic moments for the complexes of Nd(III) and Sm(III) are in close agreement with those reported in literature[9, 10]. The high melting points and insolubility of these complexes in most of the organic solvents suggest a polymeric nature for them. The bridging through phosphoryl and arsenyl groups is evident from the i.r. spectra.
Acknowledgements--One of us (GSA) is thankful to department of Atomic Energy Govt. of India and Guru Nanak University for the award of fellowship during the course of this investigation. Chemistry Department Guru Nanak University Amritsar India
S. S. SANDHU G. S. AULAKH
REFERENCES 1. D. R. Cousins and F. A. Hart, J. inorg, nucl. Chem. 30, 3009 (1968). 2. J. V. Kingston, E. M. Karankovits and R. J. Magee, Inorg. nucl. chem. Lett. 5, 485 (1969). 3. J. T. Donoghue and E. Fernandez, Bull. chem. Soc. Japan 43, 271, 932 (1970). 4. L. Genov and M. Zakharieva, Mh. Chem. 102, 687 (1971). 5. S. S. Sandhu and G. S. Aulakh, Indian J. Chem. (in press). 6. J. Chatt and F. A. Hart, J. chem. Soc. 1378 (1960). 7. P.L. Shriner and C. N. Wolf, Org. Synth. 30, 97 (1950). 8. G. E. Parris and G. G. Long, J. inorg, nucl. Chem. 32, 1593 (1970). 9. B. N. Figgis and J. Lewis, Technique of Inorganic Chemistry (Edited by H. B. Jonassen and A. Weissberger) Vol. IV, pp. 137-241. Interscience, New York (1965). 10. K. S. Krishnan and A. Mookherji, Phil. Trans. R. Soc. London A237, 135 (1938).
581
10. R. G. Bhattacharyya and D. C. Bera, Indian J. Chem. (in press). 11. R. S. Drago, D. W. Meek, M. D. Joesten and L. L. Roche, Inorg. Chem., 2, 124 (1963).
.1. inorg, nucl. Chem.. 1975,Vol. 37. p. 581. PergamonPress. Printedin Great Britain
Complexes of lanthanum(III), neodymium(III) and samarium(III) chloride with 1,2-ethylenebisdiphenylphosphine and arsine oxides (Received 2 February 1974) COMPLEXES of lanthanide(III) chlorides with a number of monotertiaryphosphine oxides[I-4] and triphenylarsine oxide[I,2] have been reported. In continuation of our previous work[5] the complexes of lanthanum(III), neodymium(III) and samarium(III) chlorides with 1,2ethylenebisdiphenylphosphine oxide (EPO) and arsine oxide (EAO) have been isolated. These complexes have been characterized with the help of elemental analysis, i.r. spectra and magnetic susceptibility data.
EXPERIMENTAL The ligands were prepared by the methods already reported in literature [6, 7]. The complexes were prepared by mixing the warm solutions of anhydrous lanthanide(III) chlorides and the ligands in 1:2 molar ratio in butanol. Carbon, hydrogen and phosphorus content of the complexes was estimated by Australian Microanalytical Service, Melbourne. Chloride was estimated by Volhard method. I.R. spectra of the complexes were recorded in nujol on i.r. 20 Beckman i.r. spectrophotometer. The magnetic susceptibility of the complexes was measured by Gouy method. RESULTS AND DISCUSSION The elemental analysis of the complexes indicate that all but one complexe correspond to the general empirical formula Ln2CI~L3-xH20 (where Ln is La(III), Nd(III) or Sm(III); L is EPO or EAO and x is 0-2). With EPO, however, neodymium(III) chloride yields NdC13. EPO,H20. The i.r. spectra of all the complexes of lanthanidc(III) chlorides with EPO record three bands near 1165, 1145 and 1085cm -~ as compared to one at ll80cm ~ in the free ligand. This splitting and downward shift in the phosphoryl stretch indicates coordination through phosphoryl oxygen. The band near 1165 and 1145 cm ~may be assigned to the coordinated but non-bridging phosphoryl group whereas the band near 1085 cm ' may be assigned to the bridging phosphoryl stretch. In the i.r. spectra of the complexes of lanthanide(III) chlorides with EAO three absorption bands are observed around 920, 880 and 850cm ~. These bands may be assigned to the coordinated arsenyl group. Since in the complexes of lanthanide(III) salts with triphenylarsine
oxide[l,2] and tribenzylarsine oxide[8] no absorption band is observed near 850 cm ~, this band may be assigned to bridging arsenyl group. The splitting in this stretch along with an upward shift has, however, been reported by other workers also[l, 2, 8]. The values of magnetic moments for the complexes of Nd(III) and Sm(III) are in close agreement with those reported in literature[9, 10]. The high melting points and insolubility of these complexes in most of the organic solvents suggest a polymeric nature for them. The bridging through phosphoryl and arsenyl groups is evident from the i.r. spectra.
Acknowledgements--One of us (GSA) is thankful to department of Atomic Energy Govt. of India and Guru Nanak University for the award of fellowship during the course of this investigation. Chemistry Department Guru Nanak University Amritsar India
S. S. SANDHU G. S. AULAKH
REFERENCES 1. D. R. Cousins and F. A. Hart, J. inorg, nucl. Chem. 30, 3009 (1968). 2. J. V. Kingston, E. M. Karankovits and R. J. Magee, Inorg. nucl. chem. Lett. 5, 485 (1969). 3. J. T. Donoghue and E. Fernandez, Bull. chem. Soc. Japan 43, 271, 932 (1970). 4. L. Genov and M. Zakharieva, Mh. Chem. 102, 687 (1971). 5. S. S. Sandhu and G. S. Aulakh, Indian J. Chem. (in press). 6. J. Chatt and F. A. Hart, J. chem. Soc. 1378 (1960). 7. P.L. Shriner and C. N. Wolf, Org. Synth. 30, 97 (1950). 8. G. E. Parris and G. G. Long, J. inorg, nucl. Chem. 32, 1593 (1970). 9. B. N. Figgis and J. Lewis, Technique of Inorganic Chemistry (Edited by H. B. Jonassen and A. Weissberger) Vol. IV, pp. 137-241. Interscience, New York (1965). 10. K. S. Krishnan and A. Mookherji, Phil. Trans. R. Soc. London A237, 135 (1938).