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Coordination compounds of diphenyl sulphoxide with tervalent gallium, indium and thallium
2808
Notes 87 511 6O0O
146
L-
233
i 40OO
== o (J
2OOO
2000
I
o
Ioo
200
300 Channel number
400
Fig. 3. Gamma spectrum of a pure arsenic fraction observed on a 10 cm 3 Ge(Li) detector. coupled to a multichannel analyser. The contribution of r°As and aaGe to the spectrum was subtracted. A Fermi-Kurie plot showed a high energy positron group with an energy of 2 . 9 5 - 0 . 0 5 MeV; this corresponded to the positron group observed by Butement and Prout. No lower energy positron groups were resolved because the housing of the plastic scintillator caused considerable back-scattering at low energies. This investigation has shown that ~gAs decays, with a half-life of 14.9-+ 0.9 min, by the emission of electromagnetic radiations of 0.087, 0.145 and 0.233 MeV respectively and positrons, of maximum energy 2-95 MeV.
Acknowledgement-We wish to express our appreciation to the staff of the Manchester Heavy Ion Linear Accelerator for performing the irradiations. University ofSalford SalfordM5 4 W T Lancashire England
J. inorg, nu¢l. Chem., 1970, Vol. 32, pp. 2808 to 2810.
G.G.J. BOSWELL T. M c G E E
Pergamon Press.
Printed in Great Britain
Coordination compounds of diphenyl sulphoxide with tervalent gallium, indium and thallium (First received 1 December 1969; in revised form 4 February 1970) DIMETHYL sulphoxide is known to form molecular addition compounds with metal ions[l, 2], but less attention has been paid to diphenyl sulphoxide. Vanlenween and Groenev[3] have reported hexa (diphenyl sulphoxide) aluminium(III) perchlorate and Lappert and Smith[4] studied the i.r. 1. 2. 3. 4.
J. Selbin, W. E. Bull and L H. Holmes, J. inorg, nucl. Chem. 16, 219 (1961). F . A . Cotton and R. Francis, J. Am. chem. Sac. 82, 2986 (1960). W . N . M . Vanleween and Groenev, Proc. Tray. Chim. Pays. Bas 75, 1173 (1966). M. F. Lappert andJ. K. Smith, J. chem. Sac. 3224 (1961).
Notes
2809
spectra of some of its adducts. An investigation of the electron donating ability of diphenyl sulphoxide to Ga(IlI), In(Ill) and TI(III) has now been carried out and seven new adducts have been prepared. EXPERIMENTAL The metal salts (perchlorates, nitrates, chlorides) were prepared by conventional methods. Diphenyl sulphoxide[5] was obtained by a Friedel Crafts reaction of benzene with thionyl chloride in the presence of anhydrous aluminium chloride and recrystallised from petroleum-ether (60-80"C). The i.r. spectra of the compounds were recorded in KBr and/or Nujol in the region 4000-400 cm -~ using a Perkin Elmer (U.S.A.) i.r. spectrophotometer model 337.
Preparation of adducts To a solution of 4.0 m-moles of M(IlI) [MOll) ~--Ga(lll), In(liD and TI(III)] salts in about 25 ml anhydrous benzene was added approximately 25 m-moles of diphenyl sulphoxide in an equal volume of anhydrous benzene and the mixture refiuxed for 4-6 hr. The solid formed was then filtered washed with benzene, and dried in vacuum for subsequent analysis. The analytical results are given in Table 1. Table 1. Experimental data for M(I 1I) diphenyl sulphoxide adducts
Compound
Analysis
M.P.
(°C)
M(II1)
C
H
l Ga(C104)a. 6DPSO
101
II Ga(NOa)s. 6DPSO
103
4-4 (4"4) 4.2 (4.7) 8.0 (8-1) 6-9 (7-0) 7-2 (7-5) 12-2 (12-7) 20.1 (20-6)
54-0 (54.0) 58.2 (58.8) 50.1 (50.6) 52.8 (53.2) 56"7 (57.1) 47.6 (48.1) 43.2 (43.7)
3"2 (3"7) 4.0 (4.2) 3.5 (3.5) 3.5 (3.7) 3.8 (3.9) 3.2 (3.3) 2.9 (3-0)
lII GaCl3.3DPSO
89
IV ln(CIO4)s. 6DPSO
108
V Ln(NOa)a. 6DPSO
115
VI lnCla. 3DPSO VII TICIa. 3DPSO
>290 107
The compounds are yellow crystalline solids soluble in ethanol and hot benzene. The compound TICI3.3DPSO is readily affected by moisture and rapidly hydrolyses on contact with HzO yielding hydrated thallium oxide. Attempts to syntbesise diphenyl suiphoxide adducts with tervalent thallium perchlorate and nitrate failed due to rapid reduction of Tl(lll) to Tl(I).
I.R. spectra Fundamental modes of vibrations observed in the i.r. spectra of the compounds and their possible assignments are listed in Table 2. Strong to very strong band centered around 1085 - 5 cm -~ consistently observed in the spectra of all the adducts is assigned to the phenyl-S stretch. In the free ligand the absorption appears as a strong band at 1090 cm -~ [6] and is therefore apparently insensitive to co-ordination. Two bands located in the region 925-995 cm -~ are assigned to ~ O stretching mode of vibration. Since this absorption in the free ligand appears at 1050cm-117], the negative shift of the band is attributed to donation of electron pair from oxygen atom of the diphenyl sulphoxide molecule to the metal atom. 5. A. Schonberg, Chem. Ber. 56, 2275 (1923). 6. R. M. Silverstein and G. C. Bassler, Spectrometric Identification of Organic Compounds p. 199. Wiley, New York (1967). 7. Bernard, D. Joyle and M. Fabian, J. chem. Soc. 2442 (1949).
Notes
2810
Table 2. I.R. s p o c t r a o f M ( I l l ) DPSO adducts Assignment Phenyl-S stretching S-~-O stretching stretching
I
I1
Ill
IV
V
Vl
VII
1090 (s, br) 995 (w) 925 (m) 680 (s)
1090 (s) 995 (w) 970 (s) 690 (s)
1080 (m) 996 (w) 940 (s) 680 (s)
1090 (s) 886 (m) 980 (s) 684 (s)
1090 (s) 965 (v.s) 945 (s) 690 (v.s)
1090 (s) 975 (s) 945 (s) 680 (s)
1085 (m) 882 (s) 950 (s) 680 (s)
s = strong, m = medium, w = weak, v = very, br = broad.
C - - S stretching vibration normally appears in the i.r. as a weak absorption in the range 700600 cm -t [8]. The weakening of the band and its variability in position mostly render its identification difficult but in this investigation it appears as a well defined absorption of strong intensity at 685___5 era-'.
,4 nionic absorption The two perchlorate adducts exhibit vibrations associated with the C104-, possessing Td symmetry and slightly broad z,3 and v4 bands of strong intensity are observed at 1100---10 and 615---5 cm -~ respectively, v3 is however partly masked by the strong phenyl-S stretching vibration located nearby. The two nitrates show absorption characteristic of ionic nitrates and the observed frequencies are listed in Table 3. Table 3. Characteristic absorption of NO3
Ga(NOs)3 • 6DPSO ln(NOs)3 • 6DPSO
NO2 asym stretching v3
NO2 stretching v~
NO2 deformation uz
Planar rock v4
1405 (v.s) 1300 (s)
1010 (s) 1010 (v.s)
822 (m) 835 (m)
715 (sh)* 722 (v.s)
• Partly masked by strong C - - H out-of-plane deformation.
,4cknowledgement-The authors express their thanks to the Head of Chemistry Department, Lucknow University, Lucknow and to the authorities of the Central Drug Research Institute, Lucknow for affording laboratory facilities and to the State CSIR, Lucknow for the award of a Junior Research Fellowship to one of the authors (G. Mohan). Authors are also indebted to Professor M. Onyszchuk of the McGill University, Montreal, Canada for a gift of gallium, indium and thallium metals.
Department of Chemistry Lucknow University Lucknow India
T.N. SRIVASTAVA G. M O H A N
8. L.J. Bellany, The lnfra RedSpectra of Complex Molecules pp. 350-366. Wiley, New York (1958).
Notes 87 511 6O0O
146
L-
233
i 40OO
== o (J
2OOO
2000
I
o
Ioo
200
300 Channel number
400
Fig. 3. Gamma spectrum of a pure arsenic fraction observed on a 10 cm 3 Ge(Li) detector. coupled to a multichannel analyser. The contribution of r°As and aaGe to the spectrum was subtracted. A Fermi-Kurie plot showed a high energy positron group with an energy of 2 . 9 5 - 0 . 0 5 MeV; this corresponded to the positron group observed by Butement and Prout. No lower energy positron groups were resolved because the housing of the plastic scintillator caused considerable back-scattering at low energies. This investigation has shown that ~gAs decays, with a half-life of 14.9-+ 0.9 min, by the emission of electromagnetic radiations of 0.087, 0.145 and 0.233 MeV respectively and positrons, of maximum energy 2-95 MeV.
Acknowledgement-We wish to express our appreciation to the staff of the Manchester Heavy Ion Linear Accelerator for performing the irradiations. University ofSalford SalfordM5 4 W T Lancashire England
J. inorg, nu¢l. Chem., 1970, Vol. 32, pp. 2808 to 2810.
G.G.J. BOSWELL T. M c G E E
Pergamon Press.
Printed in Great Britain
Coordination compounds of diphenyl sulphoxide with tervalent gallium, indium and thallium (First received 1 December 1969; in revised form 4 February 1970) DIMETHYL sulphoxide is known to form molecular addition compounds with metal ions[l, 2], but less attention has been paid to diphenyl sulphoxide. Vanlenween and Groenev[3] have reported hexa (diphenyl sulphoxide) aluminium(III) perchlorate and Lappert and Smith[4] studied the i.r. 1. 2. 3. 4.
J. Selbin, W. E. Bull and L H. Holmes, J. inorg, nucl. Chem. 16, 219 (1961). F . A . Cotton and R. Francis, J. Am. chem. Sac. 82, 2986 (1960). W . N . M . Vanleween and Groenev, Proc. Tray. Chim. Pays. Bas 75, 1173 (1966). M. F. Lappert andJ. K. Smith, J. chem. Sac. 3224 (1961).
Notes
2809
spectra of some of its adducts. An investigation of the electron donating ability of diphenyl sulphoxide to Ga(IlI), In(Ill) and TI(III) has now been carried out and seven new adducts have been prepared. EXPERIMENTAL The metal salts (perchlorates, nitrates, chlorides) were prepared by conventional methods. Diphenyl sulphoxide[5] was obtained by a Friedel Crafts reaction of benzene with thionyl chloride in the presence of anhydrous aluminium chloride and recrystallised from petroleum-ether (60-80"C). The i.r. spectra of the compounds were recorded in KBr and/or Nujol in the region 4000-400 cm -~ using a Perkin Elmer (U.S.A.) i.r. spectrophotometer model 337.
Preparation of adducts To a solution of 4.0 m-moles of M(IlI) [MOll) ~--Ga(lll), In(liD and TI(III)] salts in about 25 ml anhydrous benzene was added approximately 25 m-moles of diphenyl sulphoxide in an equal volume of anhydrous benzene and the mixture refiuxed for 4-6 hr. The solid formed was then filtered washed with benzene, and dried in vacuum for subsequent analysis. The analytical results are given in Table 1. Table 1. Experimental data for M(I 1I) diphenyl sulphoxide adducts
Compound
Analysis
M.P.
(°C)
M(II1)
C
H
l Ga(C104)a. 6DPSO
101
II Ga(NOa)s. 6DPSO
103
4-4 (4"4) 4.2 (4.7) 8.0 (8-1) 6-9 (7-0) 7-2 (7-5) 12-2 (12-7) 20.1 (20-6)
54-0 (54.0) 58.2 (58.8) 50.1 (50.6) 52.8 (53.2) 56"7 (57.1) 47.6 (48.1) 43.2 (43.7)
3"2 (3"7) 4.0 (4.2) 3.5 (3.5) 3.5 (3.7) 3.8 (3.9) 3.2 (3.3) 2.9 (3-0)
lII GaCl3.3DPSO
89
IV ln(CIO4)s. 6DPSO
108
V Ln(NOa)a. 6DPSO
115
VI lnCla. 3DPSO VII TICIa. 3DPSO
>290 107
The compounds are yellow crystalline solids soluble in ethanol and hot benzene. The compound TICI3.3DPSO is readily affected by moisture and rapidly hydrolyses on contact with HzO yielding hydrated thallium oxide. Attempts to syntbesise diphenyl suiphoxide adducts with tervalent thallium perchlorate and nitrate failed due to rapid reduction of Tl(lll) to Tl(I).
I.R. spectra Fundamental modes of vibrations observed in the i.r. spectra of the compounds and their possible assignments are listed in Table 2. Strong to very strong band centered around 1085 - 5 cm -~ consistently observed in the spectra of all the adducts is assigned to the phenyl-S stretch. In the free ligand the absorption appears as a strong band at 1090 cm -~ [6] and is therefore apparently insensitive to co-ordination. Two bands located in the region 925-995 cm -~ are assigned to ~ O stretching mode of vibration. Since this absorption in the free ligand appears at 1050cm-117], the negative shift of the band is attributed to donation of electron pair from oxygen atom of the diphenyl sulphoxide molecule to the metal atom. 5. A. Schonberg, Chem. Ber. 56, 2275 (1923). 6. R. M. Silverstein and G. C. Bassler, Spectrometric Identification of Organic Compounds p. 199. Wiley, New York (1967). 7. Bernard, D. Joyle and M. Fabian, J. chem. Soc. 2442 (1949).
Notes
2810
Table 2. I.R. s p o c t r a o f M ( I l l ) DPSO adducts Assignment Phenyl-S stretching S-~-O stretching stretching
I
I1
Ill
IV
V
Vl
VII
1090 (s, br) 995 (w) 925 (m) 680 (s)
1090 (s) 995 (w) 970 (s) 690 (s)
1080 (m) 996 (w) 940 (s) 680 (s)
1090 (s) 886 (m) 980 (s) 684 (s)
1090 (s) 965 (v.s) 945 (s) 690 (v.s)
1090 (s) 975 (s) 945 (s) 680 (s)
1085 (m) 882 (s) 950 (s) 680 (s)
s = strong, m = medium, w = weak, v = very, br = broad.
C - - S stretching vibration normally appears in the i.r. as a weak absorption in the range 700600 cm -t [8]. The weakening of the band and its variability in position mostly render its identification difficult but in this investigation it appears as a well defined absorption of strong intensity at 685___5 era-'.
,4 nionic absorption The two perchlorate adducts exhibit vibrations associated with the C104-, possessing Td symmetry and slightly broad z,3 and v4 bands of strong intensity are observed at 1100---10 and 615---5 cm -~ respectively, v3 is however partly masked by the strong phenyl-S stretching vibration located nearby. The two nitrates show absorption characteristic of ionic nitrates and the observed frequencies are listed in Table 3. Table 3. Characteristic absorption of NO3
Ga(NOs)3 • 6DPSO ln(NOs)3 • 6DPSO
NO2 asym stretching v3
NO2 stretching v~
NO2 deformation uz
Planar rock v4
1405 (v.s) 1300 (s)
1010 (s) 1010 (v.s)
822 (m) 835 (m)
715 (sh)* 722 (v.s)
• Partly masked by strong C - - H out-of-plane deformation.
,4cknowledgement-The authors express their thanks to the Head of Chemistry Department, Lucknow University, Lucknow and to the authorities of the Central Drug Research Institute, Lucknow for affording laboratory facilities and to the State CSIR, Lucknow for the award of a Junior Research Fellowship to one of the authors (G. Mohan). Authors are also indebted to Professor M. Onyszchuk of the McGill University, Montreal, Canada for a gift of gallium, indium and thallium metals.
Department of Chemistry Lucknow University Lucknow India
T.N. SRIVASTAVA G. M O H A N
8. L.J. Bellany, The lnfra RedSpectra of Complex Molecules pp. 350-366. Wiley, New York (1958).