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Addition of compounds of alkoxy antimony(V) tetrachlorides with some phosphoryl and amine-oxide ligands
J. inorg, nucL Chem., 1974,Vol.36, pp. 737-740.PergamonPress.Printedin GreatBritain.
ADDITION C O M P O U N D S OF ALKOXY ANTIMONY(V) TETRACHLORIDES WITH SOME PHOSPHORYL A N D AMINE-OXIDE LIGANDS RAM CHAND PAUL, HARMEET MADAN and S. L. CHADHA Department of Chemistry, Panjab University, Chandigarh, India (Received 12 December 1972)
Abstract--Complexes of alkoxy antimony(V) tetrachlorides, Sb(OR)CI4 (where R = CH3, CzH 5 and C2H4C1) with a variety of phosphoryl and amine-oxide ligands have been prepared and characterized by their analytical data, molecular weights, molar conductance and infrared spectra.
INTRODUCTION METAL alkoxides are known to be poor acceptors due to polymerization through alkoxy bridges so that the central metal atom acquires its favoured coordination number. It has been found that the incorporation of an electron withdrawing group in place of the alkoxy group or in the alkoxy group reduces their degree of polymerization[l] and makes the central metal atom a better acceptor[2,3]. Ethoxy antimony(V) tetrachloride has been shown to be dimeric by X-ray analysis[4], the antimony acquiring hexacoordination which is its most favoured coordination state. As no complexes of alkoxy antimony(V) tetrachlorides are known and their interaction with donor molecules has been noticed, we have tried to prepare their complexes with some phosphoryl and amine-oxide donors.
kept overnight before precipitating. The complexes of dipyridyl dioxide and 8-hydroxy quinoline N-oxide were prepared by mixing these ligands with the chloroform solution of the alkoxide and refluxing for about 1 hr. A small change in the quantities of the reacting species did not affect the composition of the complexes. As far as possible, a dry box was used for manipulations. Antimony was determined volumetrically[6]. Chloride was determined gravimetrically as silver chloride by fusion with a mixture of sodium carbonate, sodium hydroxide and potassium hydroxide and precipitating silver chloride from a nitric acid solution of the cooled melt. I.R. spectra of the complexes were examined in potassium bromide pellets or as Nujol mull films using Perkin-Elmer 337 and 521 infrared spectrophotometers. Molecular weights were determined cryoscopically and molar conductances in nitrobenzene.
RESULTS AND DISCUSSION
EXPERIMENTAL Chloroform, carbon tetrachloride, ether, phosphorus(V) oxytrichloride and hexamethylphosphoramide were purified by the usual methods. Methoxy-, ethoxy- and 2-chloroethoxy antimony(V) tetrachlorides were prepared by the addition of sulphites of the corresponding alcohols to a cold solution of antimony(V) chloride in chloroform under anhydrous conditions[5]. The solids produced were filtered, washed with carbon tetrachloride and dried under vacuum. Preparation of complexes
The complex of methoxy antimony(V) tetrachloride with hexamethylphosphoramide was prepared by mixing these reactants in equimolar quantities in chloroform. After allowing the solution to stand for an hour the solid complex was precipitated by adding dry ether. The complex w a s washed 3-4 times with ether and dried under vacuum. Other complexes were prepared similarly. For the preparation of phosphorus(V) oxytrichloride complexeswith mixtures were
As is evident from the analytical data (Table 1), the alkoxy antimony(V) tetrachloride, Sb(OR)C14 (where R = CH a, C2H~ and C2H4C1) form 1:1 (ligands: Sb(OR)CI~) addition compounds with bexamethylphosphoramide (HMPA), triphenylphosphineoxide (TPPO), trimethylphosphineoxide (TMPO), trimethylphosphate (TMP), phosphorus(V) oxytrichlodde (POCI3) , pyridine N-oxide (PY-O), ~,-,fl- and 7-pi¢oline oxides (pie-O), 8-hydroxyquinoline N-oxide (HQ-O) and 1:2 complexes with 0t,~t'-dipyridyl N-N'-dioxide (dipy-O2). These complexes are sensitive to moisture. Molecular weights of some of the complexes which have sufficient solubility in nitrobenzene indicate them to be monomeric (Table 1). Molar conductance of 10-3 M solutions of some of the complexes in nitrobenzene is of the order of 4--8 cm 2 f~- i mole- 1which suggests them to be predominantly covalent.
737
738
RAM CHANDPAUL, HARMEETMADANand S. L. CHADHA Table 1. Complexes of alkoxy antimony tetrachlorides with some phosphoryl and amine-oxide ligands Molecular Molar weight conductance* Calcu-t m.p.(°C) Reqd. Found Reqd. Found (cm2f~-~ lated Found mole- t) Sb(~o)
Complex Sb(OCH3)C1¢ . HMPA Sb(OCH3)CI , . TPPO Sb(OCH3)CI , . TMPO Sb(OCHa)C14. POC13 Sb(OCH3)CI,. TMP Sb(OCH3)C14 . Py-O Sb(OCH 3)C14. ct-Pic-O Sb(OCH3)CI 4 . fl-Pic-O Sb(OCHa)C1 * . 7-Pic-O Sb(OCH3)Cl 4 . H Q - O 2Sb(OCHa)CI,. dipy-O2 Sb(OC2Hs)CI,. HMPA Sb(OC2Hs)CI,. TPPO Sb(OC2H5)C1,. TMPO Sb(OCaHs)C1,. POCIa Sb(OC2Hs)CI,. Py-O Sb(OC2Ha)CI'4. x-Pic-O Sb(OC2Hs)CI 4 . fl-pic-O Sb(OC2Hs)C14. ?-pic-O Sb(OC2Hs)CI4. H Q - O 2Sb(OC2Hs)C14 • dipy-O2 Sb(OC2H4C1)CI,,. HMPA Sb(OC 2H4C1)C14. TPPO Sb(OC2H4CI)CI,. TMPO Sb(OC2H4CI)C14. POC13 Sb(OC2H,CI)CI4. py-O Sb(OC2H,CI)CI4. ct-pic-O Sb(OC2H4Cl)Cl,. fl-pic-O Sb(OC2H,~CI)CI,~. 7-pic-O Sb{OC2H4CI)CI~. HQ O 2Sb(OC2H4C1)Cla . dipy-O2
Colour of the solid yellow white white white liquid colourless white liquid light yellow liquid light yellow light yellow white dirtywhite yellow white white white light yellow liquid deep yellow liquid light yellow liquid light yellow white white yellow white white white white liquid light yellow liquid light yellow liquid light yellow pink white
147-48 235-37 >320 133-34
25.78 21.30 31.52 27.21 28-04
29.75 24.70 36.70 55.00 32-40
4-07 6.77
474 573
457 562
167-69
31.30 31-30 36.40 36.03 30-20 29-90 35.10 35.40
3.62
390
362
2.5
404
390
6.9
448 587
475 555
404
413
6.30 6.50
522 621
509 607
5-10
439
412
>300 169d > 300 149 300 125 71-72
>300 142d 167-68 184 >320 123-24 174
> 300 260d
25-60 21.20 31.30 27.30 28.35
CI(~o)
29.96 24.78 36.69 55.44 32.64
30.20
30.00 35.10 34.90
30.20 26.75 31.36 25.00 20.78 30.70 26.30 30.20 29.20
30.03 26.50 31.20 24.80 20-40 30.20 26.30 30.00 28.80
35.10 31.10 36.50 29.10 24.20 35.40 53.70 35.10 33.97
29.20
28.70
33-97 34.10
29.20
28.90 33.97 33.70
26.00 30.00 23.35 19.60 28.00 24-50 27.82 26.96
25.50 30-20 23.80 19.30 27-90 24-40 27.50 26.60
26.96
26.60 39.20 39.03
26.96
26-70 39,20 39.00
7-70
453
430
24.17 23.80 35.18 34.60 27.88 27.60 40.50 40.60
8.50
875
840
30.20 35.23 33.97 28.56 40.30 57.10 40.48 39-20
35.00 30-80 36.60 28.60 24.40 35.00 53.20 34.40 33.60
29.80 34.90 33.50 28.80 40.50 57.00 40.10 38.90
* As millimolar solution in nitrobenzene. t Calculated for monomeric Sb(OR)C14. L where L is the ligand.
The significant i.r. absorption frequencies for the complexes are given in Table 2. The P=O stretching frequencies[7,8] of the ligands containing phosphoryl group shift to a lower spectral region by 40-120 c m - 1 in the complexes. This indicates the coordination of these ligands through their phosphoryl oxygen atom [9] to antimony. This mode of coordination is further supported by an increase in the P - N and P - O - C stretching frequencies for H M P A and (TPPO and T M P O ) respectively. The amine-oxide ligands have characteristic vibra-
tions at nearly 1250 and 850 c m - 1 assigned to the N - O stretching and bending frequencies[10] respectively. The spectra of the complexes (Table 2) reveal the lowerLug of both the N - O stretching and bending modes as compared to those in the free lignnds. This is attributed to the coordination[ll] of these ligands through the oxygen atom of the N--O group. Apart from this, the C - H stretching (out of plane deformation of the ring) shifts to a higher frequency in the complexes which supports the above mentioned mode of coordination. In the case of the complexes of ~t,~t'-dipyridyl N,N'-
Addition compounds of alkoxy antimony(V) tetrachlorides
739
Table 2. Major infrared absorption frequencies (cm- 1) of the complexes of Sb(OR)CI* with phosphoryl and amine-oxide ligands
Compound
¢(P = O) o r V(N~)
HMPA Sb(OCH3)Ci 4 . HMPA Sb(OC2Hs)CI4. HMPA Sb(OC2H4CI)C14 . HMPA TPPO Sb(OCH3)CI 4 . TPPO Sb(OC2Hs)CI 4 . TPPO Sb(OCzH4CI)CI 4 . TPPO TMPO Sb(OCH3)C14 . TMPO Sb(OC2Hs)CI 4 . TMPO Sb(OCzH4C1)C14. TMPO POCI 3 Sb(OCH3)CI4. POCI3 Sb(OC2Hs)CI4 • POC13 Sb(OC2H4C1)Cl4. POC13 TMP Sb(OCH3)C14. TMP Py-O Sb(OCH3)C14 . Py-O
1205s 1170vs 1185vs 1180vs 1190s 1128s 1130 1120 1176s 1080s 1050s 1050s 1280s 1220s 1176s 1190s 1275s ~180s 1245s 1180vs
Sb(OC2Hs)C14 . Py-O Sb(OC2H4C1)Cb,. Py--O a-Pic-O Sb(OCH3)CI4. a-Pic-O Sb(OC2Hs)C14. ~-Pic-O Sb(OC2H,LCI)C14. ~t-pic-O fl-pic-O Sb(OCH3)C1,, . fl-pic-O Sb(OC2Hs)CI, *. fl-pic-O Sb(OC2H4CI)CI,,. fl-pic-O ~-pic-O Sb(OCH3)CI,,. ~-pic-O Sb(OC2Hs)C14.2:-pic-O Sb(OC2H,,CI)CI,* . ~-pic-O HQ-O Sb(OCH3)CI 4 . H Q - O Sb(OC2Hs)C14 . HQ-O Dipy-O2
1200vs 1180vs 1245s 1190vs 1190vs 1175vs 1280s 1200s 1180vs 1180vs 1255s 1205vs 1200vs 1180vs 1280s 1200s 1205s 1265s 1255s 1210s 1200s 1230s 1208s 1220, 1200s
2Sb(OCH3)C14. dipy-O2 2Sb(OC2Hs)C14. dipy-O2 2Sb(OC2H4C1)C14. dipy-O2
V(P--N) o r ~(N--O)
985m 988m 1000m 990 1440§ 1455 1467 1462
V(O~Sb)
•(Sb-Cl)
415 410 430sh
330vs 325s 340vs
415 422m 422m
335vs 335s 345vs 335s 340vs 335vs
485 + 494m 490s llM2s:~ 1055m 840s 820s
330vs 405m 430m 430s
332vs
440sh 395vs 430m
330vs
405s
320vs
405w
335vs
840, 830
430s
330vs
835, 820 840, 830
445, 405 440, 404, 390
340vs 328vs
815s 825s 850s 825s 820s 820s 845s 800s 790s 800s 845 825s 820s 830s 840s 810m 805m
325vs
852s, 840s
* Spectra of pure Sb(OR)C14 : Sb(OCHa)CI 4 :--1305, 1069, 1028, 879, 800, 715, 660, 612, 515s{I, 465, 388, 350, 326vs~ Sb(OCzHs)C! 4 :--1290, 1090, 1010, 970, 820, - - 613, 520vsll, 468, 385, 366, 348, 340vs$ Sb(OC2H4CI)C14 :--1270, 1065, 1025, 903, 850, 658 - 495vsl[, 460, 330-350vs$ ~" V(p_cn) . V(p~). § V(P--C).
II V(sb_o~sb). ¶ V(Sb-Ct) •
RAM CHAND PAUL, HARMEET MADAN and S. L. CHADHA
740
dioxide, the two bands corresponding to each of the N - O stretching and bending modes of the pure ligand [12] shift to lower frequencies indicating that this ligand is bidentate[13] through both of its oxygen atoms. I.R. spectra of the pure alkoxy antimony(V) tetrachlorides and their complexes in the 600-250 c m region (Table 2) reveal the presence of a strong band in the 325-346 c m - 1 region where Sb-C1 vibrations of SbCI~ occur[13-15] (v 3 of SbCI 6 in PyHSbC16 is at 336 cm-1)[13]. Apart from this, the strong bands at 515, 520 and 495 cm -1 present in the spectra of the parent methoxy, ethoxy and chloroethoxy antimony(V) tetrachlorides respectively, which are assigned to the O
Sb
Sb
vibrations[4] arc absent in the spectra of their complexes. Absence of these bands is evidently thc result of the rupture of the alkoxy bridges present in the purc alkoxides. This is further supported by the molecular weight studies.In addition to this,somc new bands have been found around 390-440 cm- i in the spectra of somc of the complexes. These bands may bc assigned to thc O--,Sb coordinate bond formed bctwccn the oxygen atom of the ligand and antimony by analogy with the earlier i.r.spectral data of the complexes of antimony(V) chloride with trimethylphosphine oxide[15].
REFERENCES
1. R. C. Paul, H. S. Makhni and S. L. Chadha, Indian J. Chem. 9, 365 (1971). 2. R. C. Paul, P. Singh, H. S. Makhni and S. L. Chadha, J. inorg, nucl. Chem. 32, 2142 (1970); Z. anorg. Chem. 377, 108 (1970); J. less-common Metals, 17, 437 (1969). 3. R. C. Paul, V. Nagpal and S. L. Chadha, lnorg. Chim. Acta 6, 335 (1972). 4. H. Preiss, Z. anorg. Chem. 362, 24 (1968). 5. A. Meuwsen and H. Mogling, Z. anorg. Chem. 285, 262 (1956). 6. A. I. Vogel, Quantitative Inorganic Analysis, 3rd Edn, p. 366. 7. E. Giesbrecht and L. B. Zinner, Inorg. nucl. Chem. Lett. 5, 575 (1969). 8. L. W. Daasch and D. C. Smith, Analyt. Chem. 23, 853 (1951). 9. J. P. Clark, V. M. Langford and C. J. Wilkins,J. chem. $oc. (A),792 (1967). I0. A. R. Katritzky and J. N. Gardner, J. chem. Soc. 2192 (1958); A. R. Katritzky and A. R. Hands. ibid. 2195 (1958). 11. N. M. Karayannis, A. N. Spece, L. L. Pytlewski and M. M. Lahia, J. Less Common Metals 22, 117 (1970). 12. A. Vinciguerra, P. G. Simpson, Y. Kakiuti and J. V. Quagliano, Inorg. Chem. 2, 286 (1963). 13. I. R. Beattie and M. Webster, J. chem. 8oc. 38 (1963). 14. R. C. Paul, H. R. Singal and S. L. Chadha, J. chem. Soc (A), 1849 (1969). 15. A. Schmidt, Z. anorg. Chem. 362, 129 (1968).
ADDITION C O M P O U N D S OF ALKOXY ANTIMONY(V) TETRACHLORIDES WITH SOME PHOSPHORYL A N D AMINE-OXIDE LIGANDS RAM CHAND PAUL, HARMEET MADAN and S. L. CHADHA Department of Chemistry, Panjab University, Chandigarh, India (Received 12 December 1972)
Abstract--Complexes of alkoxy antimony(V) tetrachlorides, Sb(OR)CI4 (where R = CH3, CzH 5 and C2H4C1) with a variety of phosphoryl and amine-oxide ligands have been prepared and characterized by their analytical data, molecular weights, molar conductance and infrared spectra.
INTRODUCTION METAL alkoxides are known to be poor acceptors due to polymerization through alkoxy bridges so that the central metal atom acquires its favoured coordination number. It has been found that the incorporation of an electron withdrawing group in place of the alkoxy group or in the alkoxy group reduces their degree of polymerization[l] and makes the central metal atom a better acceptor[2,3]. Ethoxy antimony(V) tetrachloride has been shown to be dimeric by X-ray analysis[4], the antimony acquiring hexacoordination which is its most favoured coordination state. As no complexes of alkoxy antimony(V) tetrachlorides are known and their interaction with donor molecules has been noticed, we have tried to prepare their complexes with some phosphoryl and amine-oxide donors.
kept overnight before precipitating. The complexes of dipyridyl dioxide and 8-hydroxy quinoline N-oxide were prepared by mixing these ligands with the chloroform solution of the alkoxide and refluxing for about 1 hr. A small change in the quantities of the reacting species did not affect the composition of the complexes. As far as possible, a dry box was used for manipulations. Antimony was determined volumetrically[6]. Chloride was determined gravimetrically as silver chloride by fusion with a mixture of sodium carbonate, sodium hydroxide and potassium hydroxide and precipitating silver chloride from a nitric acid solution of the cooled melt. I.R. spectra of the complexes were examined in potassium bromide pellets or as Nujol mull films using Perkin-Elmer 337 and 521 infrared spectrophotometers. Molecular weights were determined cryoscopically and molar conductances in nitrobenzene.
RESULTS AND DISCUSSION
EXPERIMENTAL Chloroform, carbon tetrachloride, ether, phosphorus(V) oxytrichloride and hexamethylphosphoramide were purified by the usual methods. Methoxy-, ethoxy- and 2-chloroethoxy antimony(V) tetrachlorides were prepared by the addition of sulphites of the corresponding alcohols to a cold solution of antimony(V) chloride in chloroform under anhydrous conditions[5]. The solids produced were filtered, washed with carbon tetrachloride and dried under vacuum. Preparation of complexes
The complex of methoxy antimony(V) tetrachloride with hexamethylphosphoramide was prepared by mixing these reactants in equimolar quantities in chloroform. After allowing the solution to stand for an hour the solid complex was precipitated by adding dry ether. The complex w a s washed 3-4 times with ether and dried under vacuum. Other complexes were prepared similarly. For the preparation of phosphorus(V) oxytrichloride complexeswith mixtures were
As is evident from the analytical data (Table 1), the alkoxy antimony(V) tetrachloride, Sb(OR)C14 (where R = CH a, C2H~ and C2H4C1) form 1:1 (ligands: Sb(OR)CI~) addition compounds with bexamethylphosphoramide (HMPA), triphenylphosphineoxide (TPPO), trimethylphosphineoxide (TMPO), trimethylphosphate (TMP), phosphorus(V) oxytrichlodde (POCI3) , pyridine N-oxide (PY-O), ~,-,fl- and 7-pi¢oline oxides (pie-O), 8-hydroxyquinoline N-oxide (HQ-O) and 1:2 complexes with 0t,~t'-dipyridyl N-N'-dioxide (dipy-O2). These complexes are sensitive to moisture. Molecular weights of some of the complexes which have sufficient solubility in nitrobenzene indicate them to be monomeric (Table 1). Molar conductance of 10-3 M solutions of some of the complexes in nitrobenzene is of the order of 4--8 cm 2 f~- i mole- 1which suggests them to be predominantly covalent.
737
738
RAM CHANDPAUL, HARMEETMADANand S. L. CHADHA Table 1. Complexes of alkoxy antimony tetrachlorides with some phosphoryl and amine-oxide ligands Molecular Molar weight conductance* Calcu-t m.p.(°C) Reqd. Found Reqd. Found (cm2f~-~ lated Found mole- t) Sb(~o)
Complex Sb(OCH3)C1¢ . HMPA Sb(OCH3)CI , . TPPO Sb(OCH3)CI , . TMPO Sb(OCHa)C14. POC13 Sb(OCH3)CI,. TMP Sb(OCH3)C14 . Py-O Sb(OCH 3)C14. ct-Pic-O Sb(OCH3)CI 4 . fl-Pic-O Sb(OCHa)C1 * . 7-Pic-O Sb(OCH3)Cl 4 . H Q - O 2Sb(OCHa)CI,. dipy-O2 Sb(OC2Hs)CI,. HMPA Sb(OC2Hs)CI,. TPPO Sb(OC2H5)C1,. TMPO Sb(OCaHs)C1,. POCIa Sb(OC2Hs)CI,. Py-O Sb(OC2Ha)CI'4. x-Pic-O Sb(OC2Hs)CI 4 . fl-pic-O Sb(OC2Hs)C14. ?-pic-O Sb(OC2Hs)CI4. H Q - O 2Sb(OC2Hs)C14 • dipy-O2 Sb(OC2H4C1)CI,,. HMPA Sb(OC 2H4C1)C14. TPPO Sb(OC2H4CI)CI,. TMPO Sb(OC2H4CI)C14. POC13 Sb(OC2H,CI)CI4. py-O Sb(OC2H,CI)CI4. ct-pic-O Sb(OC2H4Cl)Cl,. fl-pic-O Sb(OC2H,~CI)CI,~. 7-pic-O Sb{OC2H4CI)CI~. HQ O 2Sb(OC2H4C1)Cla . dipy-O2
Colour of the solid yellow white white white liquid colourless white liquid light yellow liquid light yellow light yellow white dirtywhite yellow white white white light yellow liquid deep yellow liquid light yellow liquid light yellow white white yellow white white white white liquid light yellow liquid light yellow liquid light yellow pink white
147-48 235-37 >320 133-34
25.78 21.30 31.52 27.21 28-04
29.75 24.70 36.70 55.00 32-40
4-07 6.77
474 573
457 562
167-69
31.30 31-30 36.40 36.03 30-20 29-90 35.10 35.40
3.62
390
362
2.5
404
390
6.9
448 587
475 555
404
413
6.30 6.50
522 621
509 607
5-10
439
412
>300 169d > 300 149 300 125 71-72
>300 142d 167-68 184 >320 123-24 174
> 300 260d
25-60 21.20 31.30 27.30 28.35
CI(~o)
29.96 24.78 36.69 55.44 32.64
30.20
30.00 35.10 34.90
30.20 26.75 31.36 25.00 20.78 30.70 26.30 30.20 29.20
30.03 26.50 31.20 24.80 20-40 30.20 26.30 30.00 28.80
35.10 31.10 36.50 29.10 24.20 35.40 53.70 35.10 33.97
29.20
28.70
33-97 34.10
29.20
28.90 33.97 33.70
26.00 30.00 23.35 19.60 28.00 24-50 27.82 26.96
25.50 30-20 23.80 19.30 27-90 24-40 27.50 26.60
26.96
26.60 39.20 39.03
26.96
26-70 39,20 39.00
7-70
453
430
24.17 23.80 35.18 34.60 27.88 27.60 40.50 40.60
8.50
875
840
30.20 35.23 33.97 28.56 40.30 57.10 40.48 39-20
35.00 30-80 36.60 28.60 24.40 35.00 53.20 34.40 33.60
29.80 34.90 33.50 28.80 40.50 57.00 40.10 38.90
* As millimolar solution in nitrobenzene. t Calculated for monomeric Sb(OR)C14. L where L is the ligand.
The significant i.r. absorption frequencies for the complexes are given in Table 2. The P=O stretching frequencies[7,8] of the ligands containing phosphoryl group shift to a lower spectral region by 40-120 c m - 1 in the complexes. This indicates the coordination of these ligands through their phosphoryl oxygen atom [9] to antimony. This mode of coordination is further supported by an increase in the P - N and P - O - C stretching frequencies for H M P A and (TPPO and T M P O ) respectively. The amine-oxide ligands have characteristic vibra-
tions at nearly 1250 and 850 c m - 1 assigned to the N - O stretching and bending frequencies[10] respectively. The spectra of the complexes (Table 2) reveal the lowerLug of both the N - O stretching and bending modes as compared to those in the free lignnds. This is attributed to the coordination[ll] of these ligands through the oxygen atom of the N--O group. Apart from this, the C - H stretching (out of plane deformation of the ring) shifts to a higher frequency in the complexes which supports the above mentioned mode of coordination. In the case of the complexes of ~t,~t'-dipyridyl N,N'-
Addition compounds of alkoxy antimony(V) tetrachlorides
739
Table 2. Major infrared absorption frequencies (cm- 1) of the complexes of Sb(OR)CI* with phosphoryl and amine-oxide ligands
Compound
¢(P = O) o r V(N~)
HMPA Sb(OCH3)Ci 4 . HMPA Sb(OC2Hs)CI4. HMPA Sb(OC2H4CI)C14 . HMPA TPPO Sb(OCH3)CI 4 . TPPO Sb(OC2Hs)CI 4 . TPPO Sb(OCzH4CI)CI 4 . TPPO TMPO Sb(OCH3)C14 . TMPO Sb(OC2Hs)CI 4 . TMPO Sb(OCzH4C1)C14. TMPO POCI 3 Sb(OCH3)CI4. POCI3 Sb(OC2Hs)CI4 • POC13 Sb(OC2H4C1)Cl4. POC13 TMP Sb(OCH3)C14. TMP Py-O Sb(OCH3)C14 . Py-O
1205s 1170vs 1185vs 1180vs 1190s 1128s 1130 1120 1176s 1080s 1050s 1050s 1280s 1220s 1176s 1190s 1275s ~180s 1245s 1180vs
Sb(OC2Hs)C14 . Py-O Sb(OC2H4C1)Cb,. Py--O a-Pic-O Sb(OCH3)CI4. a-Pic-O Sb(OC2Hs)C14. ~-Pic-O Sb(OC2H,LCI)C14. ~t-pic-O fl-pic-O Sb(OCH3)C1,, . fl-pic-O Sb(OC2Hs)CI, *. fl-pic-O Sb(OC2H4CI)CI,,. fl-pic-O ~-pic-O Sb(OCH3)CI,,. ~-pic-O Sb(OC2Hs)C14.2:-pic-O Sb(OC2H,,CI)CI,* . ~-pic-O HQ-O Sb(OCH3)CI 4 . H Q - O Sb(OC2Hs)C14 . HQ-O Dipy-O2
1200vs 1180vs 1245s 1190vs 1190vs 1175vs 1280s 1200s 1180vs 1180vs 1255s 1205vs 1200vs 1180vs 1280s 1200s 1205s 1265s 1255s 1210s 1200s 1230s 1208s 1220, 1200s
2Sb(OCH3)C14. dipy-O2 2Sb(OC2Hs)C14. dipy-O2 2Sb(OC2H4C1)C14. dipy-O2
V(P--N) o r ~(N--O)
985m 988m 1000m 990 1440§ 1455 1467 1462
V(O~Sb)
•(Sb-Cl)
415 410 430sh
330vs 325s 340vs
415 422m 422m
335vs 335s 345vs 335s 340vs 335vs
485 + 494m 490s llM2s:~ 1055m 840s 820s
330vs 405m 430m 430s
332vs
440sh 395vs 430m
330vs
405s
320vs
405w
335vs
840, 830
430s
330vs
835, 820 840, 830
445, 405 440, 404, 390
340vs 328vs
815s 825s 850s 825s 820s 820s 845s 800s 790s 800s 845 825s 820s 830s 840s 810m 805m
325vs
852s, 840s
* Spectra of pure Sb(OR)C14 : Sb(OCHa)CI 4 :--1305, 1069, 1028, 879, 800, 715, 660, 612, 515s{I, 465, 388, 350, 326vs~ Sb(OCzHs)C! 4 :--1290, 1090, 1010, 970, 820, - - 613, 520vsll, 468, 385, 366, 348, 340vs$ Sb(OC2H4CI)C14 :--1270, 1065, 1025, 903, 850, 658 - 495vsl[, 460, 330-350vs$ ~" V(p_cn) . V(p~). § V(P--C).
II V(sb_o~sb). ¶ V(Sb-Ct) •
RAM CHAND PAUL, HARMEET MADAN and S. L. CHADHA
740
dioxide, the two bands corresponding to each of the N - O stretching and bending modes of the pure ligand [12] shift to lower frequencies indicating that this ligand is bidentate[13] through both of its oxygen atoms. I.R. spectra of the pure alkoxy antimony(V) tetrachlorides and their complexes in the 600-250 c m region (Table 2) reveal the presence of a strong band in the 325-346 c m - 1 region where Sb-C1 vibrations of SbCI~ occur[13-15] (v 3 of SbCI 6 in PyHSbC16 is at 336 cm-1)[13]. Apart from this, the strong bands at 515, 520 and 495 cm -1 present in the spectra of the parent methoxy, ethoxy and chloroethoxy antimony(V) tetrachlorides respectively, which are assigned to the O
Sb
Sb
vibrations[4] arc absent in the spectra of their complexes. Absence of these bands is evidently thc result of the rupture of the alkoxy bridges present in the purc alkoxides. This is further supported by the molecular weight studies.In addition to this,somc new bands have been found around 390-440 cm- i in the spectra of somc of the complexes. These bands may bc assigned to thc O--,Sb coordinate bond formed bctwccn the oxygen atom of the ligand and antimony by analogy with the earlier i.r.spectral data of the complexes of antimony(V) chloride with trimethylphosphine oxide[15].
REFERENCES
1. R. C. Paul, H. S. Makhni and S. L. Chadha, Indian J. Chem. 9, 365 (1971). 2. R. C. Paul, P. Singh, H. S. Makhni and S. L. Chadha, J. inorg, nucl. Chem. 32, 2142 (1970); Z. anorg. Chem. 377, 108 (1970); J. less-common Metals, 17, 437 (1969). 3. R. C. Paul, V. Nagpal and S. L. Chadha, lnorg. Chim. Acta 6, 335 (1972). 4. H. Preiss, Z. anorg. Chem. 362, 24 (1968). 5. A. Meuwsen and H. Mogling, Z. anorg. Chem. 285, 262 (1956). 6. A. I. Vogel, Quantitative Inorganic Analysis, 3rd Edn, p. 366. 7. E. Giesbrecht and L. B. Zinner, Inorg. nucl. Chem. Lett. 5, 575 (1969). 8. L. W. Daasch and D. C. Smith, Analyt. Chem. 23, 853 (1951). 9. J. P. Clark, V. M. Langford and C. J. Wilkins,J. chem. $oc. (A),792 (1967). I0. A. R. Katritzky and J. N. Gardner, J. chem. Soc. 2192 (1958); A. R. Katritzky and A. R. Hands. ibid. 2195 (1958). 11. N. M. Karayannis, A. N. Spece, L. L. Pytlewski and M. M. Lahia, J. Less Common Metals 22, 117 (1970). 12. A. Vinciguerra, P. G. Simpson, Y. Kakiuti and J. V. Quagliano, Inorg. Chem. 2, 286 (1963). 13. I. R. Beattie and M. Webster, J. chem. 8oc. 38 (1963). 14. R. C. Paul, H. R. Singal and S. L. Chadha, J. chem. Soc (A), 1849 (1969). 15. A. Schmidt, Z. anorg. Chem. 362, 129 (1968).