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Mixed ligand (diisobutoxyphosphato-chloro) titanium(III), uranium(IV) and thorium(IV) complexes
2102
Notes
free ligand value. This indicates that the covalent interaction between metal and carboxylate group is less and the band is more of electrostatic type. Bands at 1600-1400 cm -1 correspond to catechol and pyridine ring stretching modes. The bands at nearly 1400 cm -~ and nearly 1250 cm-' correspond to deformation and wagging of -CH~ group. The C - C stretching band occurs in the region nearly 1200-1000 cm -~. Bands obtained in the region 900-750 cm -~ correspond to ring and C - H out of plane deformation. The band at 720 cm -1 corresponds to C-S stretching vibration. The two lowest frequency bands of pyridine 605 and 405 cm -~ suffer significant shifts to higher frequency upon complex formation [13]. In case of our quaternary complexes the bands at 640 and 450 may be due to corresponding pyridine bands. The bands at 400 and 425 cm -1 correspond to M - O (metal-catechol) stretching and M-S stretching, respectively. Due to weak interaction between metal and tertiary bases M - N frequency may occur at lower frequency and could not be obtained.
Acknowledgements- Our thanks are due to Prof. S. M. Sethna, Head of the Chemistry Department, M. S. University of Baroda, Baroda-2, for providing necessary laboratory facilities, and also to the U.G.C., New Delhi, for award of Jr. Research Fellowship to C.R.J.
C. R. J E J U R K A R
Chemistry Department Faculty of Science M.S. University Baroda-2, India
P. K. B H A T T A C H A R Y A
13. David M. Adams, Metal-ligand and Related Vibrations, p. 278. Edward Arnold, London (1967).
J. inorg, nucl. Chem., 1973, Vol. 35, pp. 2102-2104.
Pergamon Press.
Printed in Great Britain
Mixed ligand (diisobutoxyphosphato-chloro) titanium(HI), uranium(IV) and thorium(IV) complexes (Received 23 August 1972) REACTIONSbetween neutral phosphate or phosphonate esters of the types (RO)3P=O and (RO)2RP=O, respectively (where R = CH3, C2H5, n-C3HT, i-C3H7 or n-C4Ho), with MC13 (M =AI, Ga, In, Sc, Y, Ln, Ti, V, Cr, Fe) or MCI4 (M = U, Th) at elevated temperatures resuR in the precipitation of polynuclear complexes of the general type MLn (L = (RO)2POO- or (RO)RPOO-; n = 3 or 4), involving bridging - O - P - O - bidentate ligand groups between neighboring metal ions [1]. Similar reactions between triisobutyl phosphate (TIBP) and the above metal chlorides are herein reported: MCI3 (M = AI, Ga, In, Sc, Y, Ln, V, Cr, Fe) salts react with TIBP at 100°-200°C, yielding the corresponding tris(diisobutoxyphosphato) M(III) (M(DIBP)3) complexes, as was expected [1]. The properties of these complexes will be reported elsewhere [2]. TiCla, UC14 or ThC14, however, reactions with TIBP, under similar conditions, lead to the precipitation of mixed ligand complexes, involving coordination of both chloro and DIBP groups. Thus, UC14 and ThC14 yield chlorotris-(diisobutoxyphosphato) M(IV) complexes and a mixture of isobutyl chloride, HC1 and butene upon reaction with TIBP at 100 °1. C. M. Mikulski, N. M. Karayannis, M. J. Strocko, L. L. Pytlewski and M. M. Labes, lnorg. Chem. 9, 2053 (1970); N. M. Karayannis, C. M. Mikulski, M. J. Strocko, L. L. Pytlewski and M. M. Labes, lnorg, chim. Acta 4, 455 (1970); C. M. Mikulski, N. M. Karayannis and L. L. Pytlewski, 161st. National Meetg., Am. Chem. Soc., Los Angeles, California, March 28-April 2, 1971; see Abstracts No. PHYS 73. 2. C. M. Mikulski, N. M. Karayannis and L. L. Pytlewski, To be published.
Notes
2103
200°C. TiCh, on the other hand, reacts with T I B P under the same conditions, to form dichloro (diisobutoxyphosphato) Ti(III) as final product, via a white paramagnetic intermediate, analyzing as follows: C10.49%, H 2.99%, P 1.27%, Ti 39.28%. The volatile reaction products were again i-C4HoCI, HC1 and butene. Experimentally, the anhydrous metal chlorides were suspended in excess TIBP at room temperature, and the temperature of the reactions mixture was gradually increased. At 50°-70°C, the metal chloride dissolved in TIBP, and at higher temperatures (> 100°C) formation of precipitates was observed. In the case of UC14 and ThCI4 reactions with TIBP, which were carried out in the atmosphere [1], M(DIBP)3CI complexes were obtained. The TiCIr-TIBP reaction was conducted in the drybox under a nitrogen atmosphere [1]; during this reaction the white intermediate mentioned above precipitated at 140°C, but was redissolved at higher temperatures in the supernatant liquid, and the resulting solution yielded Ti(DIBP)CI~ at 165°C. The new complexes were filtered, thoroughly washed with ether and acetone and dried in an evacuated desiccator over CaCI2. The formulation of these compounds as M(DIBP)aCI (M = U, Th) and Ti(DIBP)CI2 is supported by analytical (A. Bernhardt Mikroanalytisches Laboratorium, Elbach, W. Germany) and i.r. data (cf. Table 1). In fact, in addition to the Vpoo(asymmetric and symmetric) and metal sensitive (tentatively assigned as primarily VM-O) bands, which are characteristic of dialkoxyphosphato - M ( I l I ) and -M(IV) complexes[l], VM-ct bands were tentatively identified in the 280-250 cm -1 region[3, 4]. Bands in this region are not observed in M(DIBP)3 complexes ( M = A I , Ga, In, Sc, Y, Ln, V, Cr, Fe)[2]. Magnetic moments (Table 1) of the Ti 3÷ and U a+ complexes are within the normal range of values for compounds of these metal ions [5]. The electronic spectrum of Ti(DIBP)CI2 is suggestive of a hexacoordinated conTable 1. Analyses, spectral and magnetic data for Ti(DIBP)C12 and M(DIBP)3CI (M=U, Th) complexes Analyses
Ti(DIBP)C12
U(DIBP)3CI
Th(DIBP)3CI
29.30,5.52,9.45, 14.60, 21-62 30.26, 5.94, 10.09, 15.37, 20.80
31.96,6.03, 10.30, 26.39, 3.93 31.99, 6.20, 10.01, 26.84, 3.47
32.17,6-07, 10.37, 25.89, 3-95 32.02, 6.24, 10.15, 26-12, 3.99
Tan
Light green
White
1150 s, sh 1101 vs 527s,418m,315w, b
1152 s, b 1096 s 5 2 1 s , 4 1 1 m , 312w, b
vM-cl
1161 s, sh 1080 s, sh 531s, 420m, sh, 295 m 281 m
260 m
259 m
106 Xmc°r, cgsu /-~efr,BM (298°K)
867 1"70
3129 2"74
diamagnetic
Electronic spectra
< 300 vs, 542 s, sh, 626 m, sh
441 vs, 477 m, 531 m, 584 m, 646 s, 760 w, b, 880 m, b, 1090 vs, 1404 m, 1590 w, b
Calc%, C, H, P,M, Ct Found%, C, H, P, M, CI
Color I.R. data cm -x* vpoo, asym V~,oo,sym VM-O
hmax, nm
*Spectra (i.r. and electronic) obtained on Nujol mulls. I.R. spectra do not exhibit coordinated water bands. Abbreviations: s, strong; m, medium; w, weak; v, very; b, broad; sh, shoulder. 3. D. M. Adams, J. Chatt, J. M. Davidson and J. Gerratt, J. chem. Soc.. 2189 (1963). 4. D. A. James and M. J. Nolan, lnorg, nucl. Chem. Lett. 4, 97 (1968).
2104
Notes
figuration for this complex [1], while U(DIBP)3CI exhibits an electronic spectrum typical of U(IV) compounds[l] (Table 1). The new complexes are insoluble in water and all common organic solvents, as is generally the case with polynuclear dialkoxyphosphato or alkoxy alkylphosphonato-M(III) or M(IV) complexes [1, 2]. It appears, therefore, that the mixed ligand complexes reported here are also polymeric, involving exclusively bridging DIBP and chloro iigands. The Ti(III) complex is hexacoordinated (vide supra), whereas the U(IV) and Th(IV) complexes most probably involve coordination number 8 for the central metal ions [ 1,2]. The stabilization of complexes of the type M(DIBP)mCI~ rather than M(DIBP)sor4 in the cases reported is presumably due to the steric effects of the isobutyl groups of the DIBP ligand. Apparently, the reaction [ 1,2, 6] MCIn + n(RO).~P=O ~ M [(RO2)POO]n + nRCI proceeds stepwise and involves intermediates of the types M [(RO)zPOO]~,Cln-m, as suggested by the isolation of the complexes reported. The white intermediate formed during the TiCIs-TIBP reaction cannot be characterized on the basis of the available evidence. In fact the C: P ratio (8.26) analytically determined (vide supra) is even higher than that corresponding to TIBP (4.65), while the small quantities of this compound available were not sufficient for chlorine determination. Titanium is apparently in the + 3 oxidation state in this product, which is paramagnetic (106Xu = 2.83 cgsu at 298°K), as already mentioned.
Department of Chemistry Drexel University Philadelphia, P a. 19104
C. M. M I K U L S K I L. L. PYTLEWSKI
Amoco Chemicals Corporation Naperville Illinois
N. M. K A R A Y A N N I S
5. B. N. Figgis and J. Lewis, Prog. inorg. Chem. 6, 37 (1964); B. Jezowska-Trzebiatowska and K. Bukietynska, In Theory and Structure of Complex Compounds, pp. 311-314. Macmillan, New York (1964). 6. V. Guttmarm and G. Beer, lnorg, chim. Acta 3, 87 (1969).
J. inorg, nucl. Chem., 1973, Vol. 35, pp. 2104-2106.
Pergamon Press.
Printed in Great Britain
Infrared spectra and magnetic susceptibifity of some amino Ni(ID oxalate
complexes of
(Received 2 August 1972) A SERIES of coordination compounds through a reaction of some primary and secondary amines with Ni(I1) oxalate were prepared. Investigations such as analysis of the compounds, their magnetic susceptibility and a discussion of the i.r. spectra in the region 4000-700 cm -1 have been carded out to resolve their structural information in terms of symmetry and nature of coordination.
Notes
free ligand value. This indicates that the covalent interaction between metal and carboxylate group is less and the band is more of electrostatic type. Bands at 1600-1400 cm -1 correspond to catechol and pyridine ring stretching modes. The bands at nearly 1400 cm -~ and nearly 1250 cm-' correspond to deformation and wagging of -CH~ group. The C - C stretching band occurs in the region nearly 1200-1000 cm -~. Bands obtained in the region 900-750 cm -~ correspond to ring and C - H out of plane deformation. The band at 720 cm -1 corresponds to C-S stretching vibration. The two lowest frequency bands of pyridine 605 and 405 cm -~ suffer significant shifts to higher frequency upon complex formation [13]. In case of our quaternary complexes the bands at 640 and 450 may be due to corresponding pyridine bands. The bands at 400 and 425 cm -1 correspond to M - O (metal-catechol) stretching and M-S stretching, respectively. Due to weak interaction between metal and tertiary bases M - N frequency may occur at lower frequency and could not be obtained.
Acknowledgements- Our thanks are due to Prof. S. M. Sethna, Head of the Chemistry Department, M. S. University of Baroda, Baroda-2, for providing necessary laboratory facilities, and also to the U.G.C., New Delhi, for award of Jr. Research Fellowship to C.R.J.
C. R. J E J U R K A R
Chemistry Department Faculty of Science M.S. University Baroda-2, India
P. K. B H A T T A C H A R Y A
13. David M. Adams, Metal-ligand and Related Vibrations, p. 278. Edward Arnold, London (1967).
J. inorg, nucl. Chem., 1973, Vol. 35, pp. 2102-2104.
Pergamon Press.
Printed in Great Britain
Mixed ligand (diisobutoxyphosphato-chloro) titanium(HI), uranium(IV) and thorium(IV) complexes (Received 23 August 1972) REACTIONSbetween neutral phosphate or phosphonate esters of the types (RO)3P=O and (RO)2RP=O, respectively (where R = CH3, C2H5, n-C3HT, i-C3H7 or n-C4Ho), with MC13 (M =AI, Ga, In, Sc, Y, Ln, Ti, V, Cr, Fe) or MCI4 (M = U, Th) at elevated temperatures resuR in the precipitation of polynuclear complexes of the general type MLn (L = (RO)2POO- or (RO)RPOO-; n = 3 or 4), involving bridging - O - P - O - bidentate ligand groups between neighboring metal ions [1]. Similar reactions between triisobutyl phosphate (TIBP) and the above metal chlorides are herein reported: MCI3 (M = AI, Ga, In, Sc, Y, Ln, V, Cr, Fe) salts react with TIBP at 100°-200°C, yielding the corresponding tris(diisobutoxyphosphato) M(III) (M(DIBP)3) complexes, as was expected [1]. The properties of these complexes will be reported elsewhere [2]. TiCla, UC14 or ThC14, however, reactions with TIBP, under similar conditions, lead to the precipitation of mixed ligand complexes, involving coordination of both chloro and DIBP groups. Thus, UC14 and ThC14 yield chlorotris-(diisobutoxyphosphato) M(IV) complexes and a mixture of isobutyl chloride, HC1 and butene upon reaction with TIBP at 100 °1. C. M. Mikulski, N. M. Karayannis, M. J. Strocko, L. L. Pytlewski and M. M. Labes, lnorg. Chem. 9, 2053 (1970); N. M. Karayannis, C. M. Mikulski, M. J. Strocko, L. L. Pytlewski and M. M. Labes, lnorg, chim. Acta 4, 455 (1970); C. M. Mikulski, N. M. Karayannis and L. L. Pytlewski, 161st. National Meetg., Am. Chem. Soc., Los Angeles, California, March 28-April 2, 1971; see Abstracts No. PHYS 73. 2. C. M. Mikulski, N. M. Karayannis and L. L. Pytlewski, To be published.
Notes
2103
200°C. TiCh, on the other hand, reacts with T I B P under the same conditions, to form dichloro (diisobutoxyphosphato) Ti(III) as final product, via a white paramagnetic intermediate, analyzing as follows: C10.49%, H 2.99%, P 1.27%, Ti 39.28%. The volatile reaction products were again i-C4HoCI, HC1 and butene. Experimentally, the anhydrous metal chlorides were suspended in excess TIBP at room temperature, and the temperature of the reactions mixture was gradually increased. At 50°-70°C, the metal chloride dissolved in TIBP, and at higher temperatures (> 100°C) formation of precipitates was observed. In the case of UC14 and ThCI4 reactions with TIBP, which were carried out in the atmosphere [1], M(DIBP)3CI complexes were obtained. The TiCIr-TIBP reaction was conducted in the drybox under a nitrogen atmosphere [1]; during this reaction the white intermediate mentioned above precipitated at 140°C, but was redissolved at higher temperatures in the supernatant liquid, and the resulting solution yielded Ti(DIBP)CI~ at 165°C. The new complexes were filtered, thoroughly washed with ether and acetone and dried in an evacuated desiccator over CaCI2. The formulation of these compounds as M(DIBP)aCI (M = U, Th) and Ti(DIBP)CI2 is supported by analytical (A. Bernhardt Mikroanalytisches Laboratorium, Elbach, W. Germany) and i.r. data (cf. Table 1). In fact, in addition to the Vpoo(asymmetric and symmetric) and metal sensitive (tentatively assigned as primarily VM-O) bands, which are characteristic of dialkoxyphosphato - M ( I l I ) and -M(IV) complexes[l], VM-ct bands were tentatively identified in the 280-250 cm -1 region[3, 4]. Bands in this region are not observed in M(DIBP)3 complexes ( M = A I , Ga, In, Sc, Y, Ln, V, Cr, Fe)[2]. Magnetic moments (Table 1) of the Ti 3÷ and U a+ complexes are within the normal range of values for compounds of these metal ions [5]. The electronic spectrum of Ti(DIBP)CI2 is suggestive of a hexacoordinated conTable 1. Analyses, spectral and magnetic data for Ti(DIBP)C12 and M(DIBP)3CI (M=U, Th) complexes Analyses
Ti(DIBP)C12
U(DIBP)3CI
Th(DIBP)3CI
29.30,5.52,9.45, 14.60, 21-62 30.26, 5.94, 10.09, 15.37, 20.80
31.96,6.03, 10.30, 26.39, 3.93 31.99, 6.20, 10.01, 26.84, 3.47
32.17,6-07, 10.37, 25.89, 3-95 32.02, 6.24, 10.15, 26-12, 3.99
Tan
Light green
White
1150 s, sh 1101 vs 527s,418m,315w, b
1152 s, b 1096 s 5 2 1 s , 4 1 1 m , 312w, b
vM-cl
1161 s, sh 1080 s, sh 531s, 420m, sh, 295 m 281 m
260 m
259 m
106 Xmc°r, cgsu /-~efr,BM (298°K)
867 1"70
3129 2"74
diamagnetic
Electronic spectra
< 300 vs, 542 s, sh, 626 m, sh
441 vs, 477 m, 531 m, 584 m, 646 s, 760 w, b, 880 m, b, 1090 vs, 1404 m, 1590 w, b
Calc%, C, H, P,M, Ct Found%, C, H, P, M, CI
Color I.R. data cm -x* vpoo, asym V~,oo,sym VM-O
hmax, nm
*Spectra (i.r. and electronic) obtained on Nujol mulls. I.R. spectra do not exhibit coordinated water bands. Abbreviations: s, strong; m, medium; w, weak; v, very; b, broad; sh, shoulder. 3. D. M. Adams, J. Chatt, J. M. Davidson and J. Gerratt, J. chem. Soc.. 2189 (1963). 4. D. A. James and M. J. Nolan, lnorg, nucl. Chem. Lett. 4, 97 (1968).
2104
Notes
figuration for this complex [1], while U(DIBP)3CI exhibits an electronic spectrum typical of U(IV) compounds[l] (Table 1). The new complexes are insoluble in water and all common organic solvents, as is generally the case with polynuclear dialkoxyphosphato or alkoxy alkylphosphonato-M(III) or M(IV) complexes [1, 2]. It appears, therefore, that the mixed ligand complexes reported here are also polymeric, involving exclusively bridging DIBP and chloro iigands. The Ti(III) complex is hexacoordinated (vide supra), whereas the U(IV) and Th(IV) complexes most probably involve coordination number 8 for the central metal ions [ 1,2]. The stabilization of complexes of the type M(DIBP)mCI~ rather than M(DIBP)sor4 in the cases reported is presumably due to the steric effects of the isobutyl groups of the DIBP ligand. Apparently, the reaction [ 1,2, 6] MCIn + n(RO).~P=O ~ M [(RO2)POO]n + nRCI proceeds stepwise and involves intermediates of the types M [(RO)zPOO]~,Cln-m, as suggested by the isolation of the complexes reported. The white intermediate formed during the TiCIs-TIBP reaction cannot be characterized on the basis of the available evidence. In fact the C: P ratio (8.26) analytically determined (vide supra) is even higher than that corresponding to TIBP (4.65), while the small quantities of this compound available were not sufficient for chlorine determination. Titanium is apparently in the + 3 oxidation state in this product, which is paramagnetic (106Xu = 2.83 cgsu at 298°K), as already mentioned.
Department of Chemistry Drexel University Philadelphia, P a. 19104
C. M. M I K U L S K I L. L. PYTLEWSKI
Amoco Chemicals Corporation Naperville Illinois
N. M. K A R A Y A N N I S
5. B. N. Figgis and J. Lewis, Prog. inorg. Chem. 6, 37 (1964); B. Jezowska-Trzebiatowska and K. Bukietynska, In Theory and Structure of Complex Compounds, pp. 311-314. Macmillan, New York (1964). 6. V. Guttmarm and G. Beer, lnorg, chim. Acta 3, 87 (1969).
J. inorg, nucl. Chem., 1973, Vol. 35, pp. 2104-2106.
Pergamon Press.
Printed in Great Britain
Infrared spectra and magnetic susceptibifity of some amino Ni(ID oxalate
complexes of
(Received 2 August 1972) A SERIES of coordination compounds through a reaction of some primary and secondary amines with Ni(I1) oxalate were prepared. Investigations such as analysis of the compounds, their magnetic susceptibility and a discussion of the i.r. spectra in the region 4000-700 cm -1 have been carded out to resolve their structural information in terms of symmetry and nature of coordination.