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Complexes of titanium(IV) chloride alkoxides with oxygen and nitrogen bases
Journal of the Less-Common Metals Elsevier Sequoia S.A., Lausanne - Printed in The Netherlands
COMPLEXES OF TITANIUM(IV) CHLORIDE OXYGEN AND NITROGEN BASES
Ii. C. PAUL,
H. S. MAKHNI,
P. SINGH
AND
ALKOXIDES
137
WITH
S. L. CHADHA
Department of Chemistry, Panjab University. Chandigavh-Iq (India) (Received
October z8th, 1968; revised December
Ioth, 1968)
SUMMARY
Solid coordination complexes of titanium(IV) chloride alkoxides with dimethylsulfoxide, dimethylformamide, N-methylacetamide, pyridine, and ethylenediamine have been prepared. Infrared spectra of these complexes indicate that the oxygen and nitrogen atoms, of the sulphoxide and amides, and the nitrogen bases, respectively, coordinate to titanium.
INTRODUCTIOE
Amides, sulfoxides and nitrogen bases are known to form addition compounds with a number of metal halide+-4, and oxyhalide+7. Infrared spectra of a few of these indicate the coordination of the oxygen atoms of the ligands to the metal atoms.-a. Complexes of titanium(IV) chloride have also been reported with amidess. Addition compounds of titanium(IV) chloride alkoxides with donors have not been reported except with alcohols9 and a I : I compound of titanium(IV) chloride triethoxide with dimethylsulfoxidelo. The present communication describes the preparation and study of the infra-red spectra of complexes of titanium(IV) chloride alkoxides, TiClz(OR)z, [R=Me, Et, Pm, Pri, Bu 12,Buil and of titanium monochloride tris(z-chloroethoxide) with some oxygen and nitrogen bases. EXPERIMENTAL
Benzene, ether, dimethylsulfoxide, dimethylformamide, N-methylacetamide, pyridine, ethylenediamine and alcohols were purified by standard methods. Titanium(IV) chloride alkoxides were prepared as described in the literatureg. Preparation of complexes To a solution of the alkoxide in benzene, an equimolar proportion of the ligand in the same solvent was added. Usually, a viscous layer separated out which was washed with benzene and subsequently subjected to reduced pressure. The product was then treated with dry ether when a crystalline compound was obtained. This was repeatedly washed with ether and dried under vacuum. .I. Less-Common Metals, 17 (1969) 437-441
R. C. PAUL, H. S. MAKHNI, P. SINGH, S. L. CHADHA
438
Titanium was determined as described by BRADLEY et al.11 and the chloride content was obtained following fusion with sodium carbonate and potassium hydroxide, silver chloride being precipitated from a nitric acid solution of the cooled melt. Infrared spectra of the complexes were examined as nujol mull films using a Perkin Elmer-337 infrared spectrophotometer. RESULTS AND DISCUSSION Titanium(IV)
chloride
Bu”), and titanium
alkoxide
monochloride
(DMSO), dimethylformamide ethylenediamine (en) with
assigned
By analogy
a hexa
(R=Me,
most form
with
coordination
these,
Et,
react
(DMF), N-methylacetamide the formation of solid addition
results (Table I) indicate that Titanium(IV) chloride alkoxides are dimericls.
TiCls(OR)s
tris(z-chloroethoxide),
titanium them
in the
Pr”, Bun,
and
(NMA), pyridine (Py) and compounds. The analytical
of the complexes have I : I addition compounds
by assuming
Pm,
with dimethylsulfoxide
a I: I stoichiometry. with alcohols9 which
present
to be dimeric.
complexes Cryoscopic
may
be
measure-
TABLE I cCILOURAND NMA
AND
ANALYTICAL
PYRIDINE
AND
DATA
OF THE
Compound
TiClz(OMe)s. DMSO TiClz(OMe)s.DMF TiClz(OMe)z.NMA TiClz(OMe)z+ zen TiClz(OEt)z. DMSO TiClz(OEt)za DMF TiClz(OPr‘)z. DMSO TiClz(OPr’)s. DMF TiClz(OPr”) 2. NMA TiClz(OPr”)z.Py TiClz(OPr’) . en TiClz(OPrn)z. DMSO TiClz(OPrn)z. DMF TiClt(OPrn)2. zPy TiClz(OBu‘)z. DMSO TiClz(OBu’)x. DMF TiCls(OBu’)z. NMA TiClz(OBun)z. DMSO TiClz(OBun)s. DMF TiCl(OC%H&l)3. DMF TiCl(OCsH4Cl)s. NMA TiCl(OCzH&l)z. en
~eSS-COM9aOW
ibfetak,
OF TITANIUM
ALKOXIDE
WITH
DMSO,
DMF,
Found
(%)
Colour and
Required
state
Ti
Cl
Ti
Cl
Yellow viscous Yellow powder Yellow viscous Yellow solid White crystals Yellowish-white crystals White solid Yellow powder Yellow powder Yellowish powder White White crystals Yellowish-white crystals White solid White solid Yellowish-white solid Yellow crystals White solid White solid Yellowish solid Yellowish solid White powder
18.53 18.92 18.92 16.92 16.72 17.02
27.42 27.96 27.96 23.60
18.26
27.35
18.73
27.89
* All the complexes decompose J.
COMPLEXES*
ETHYLENEDIAMINE
17
(1969)
18.86
27.48
16.85
23.25
24.74 25.19
16.23
24.83
16.92
24.98
15.24 15.48 15.48 15.17
22.24 22.91
15.13
22.42
15.37
22.83
22.91
‘5.40
22.79
22.48
15.18
22.38
16.14
23.92 22.54
16.25
23.52
15.21
22.31
22.91
15.36
22.81
17.9 20.70
II.95
17.62
X4.00
13.88
20.62
14.20
21.01
14.12
20.89
14.20
21.01
14.25
20.91
14.00
20.70
14.13
20.62
14.20
21.01
14.17
21.21
12.15
35.95 35.95 37.43
12.01
35.87
12.31
35.68
12.68
36.82
15.24 15.48 12.13
12.15 12.63
before reaching their melting points. 437-441
(%)
COMPLEXES
OF Ti(IV)
CHLORIDE
0 ANI) N BASES
ALKOXIDESWITH
439
ments for the determination of the molecularity of these complexes could not be carried out on account of their insolubility in common organic solvents. The I: I complexes, therefore, may be tentatively represented as donor 7 \ R_.~lTiJ”\Ti c,’
CZ-R ‘Of k
‘Cl i donor
Infrared spectra have been recorded from 4000 to 600 cm-l, the important bands are given in Table II. The N-H stretching band of pure NMA at 3280 cm-l moves to a higher spectral region in its complexes with titanium(IV) chloride alkoxides. The trend of the shift is in line with the corresponding shift discussed in the complexes of NMA with metal halides3, and oxyhalides5, which suggests that the nitrogen atom of this amide is not the donor. NMA and DMF exhibit the amide-I band at 1650-1680 cm-1 while the amideII band of NMA is present at 1550 cm-l. These bands shift to a lower spectral region in the complexes of these amides; this shift establishes that the carbonyl oxygen coordinates to titanium(W) chloride alkoxides and it is in agreement with the observations made regarding the complexes of amides with metal halides’-33”. The spectral bands of the amides in the 1100-1300 cm-1 region assigned to the vibrations of the C-N group, shift to a higher spectral region in the complexes; this also supports coordination by the carbonyl oxygen of the amide. DMF has a spectral band at 655 cm-l, due to the N-C=0 bending frequency. This band shifts to the higher spectral region at 680 cm-l, which is in agreement with the observations made by JUNGBAUR A~W CURRANTS. Y (S =0) of pure DMSO, present at 1050 cm-l, shifts to a lower spectral region by 40-60 cm-l in the spectra of the complexes of DMSO with titanium(W) chloride alkoxides. This indicates the coordination of DMSO through its oxygen atom and is in agreement with the observation by COTTOY et ~1.14.The Y (C-S) of DMSO, lying at 660 cm-1 and 690 cm- 1, shift to a higher spectral region in the spectra of its complexes which further confirms the coordination of DMSO through the oxygen atom. Comparison of the significant infra-red spectral bands of pyridine and its complexes with titanium(IV) chloride alkoxide (Table II) indicates that the bands due to C-C and C-N stretching frequencies shift to a higher spectral region. The ring vibrational bands of pyridine at 1005 cm-1 and 600 cm-l shift to 1025 and 625 cm-l,
respectively.
These
observations
may
be interpreted
in terms
of the
pyridine nitrogen acting as the donor, and they are in agreement with the observations by GILL et a1.15, GREENWooD AND WADERS and PAUL AND CHADHA~~. The spectra of the complexes (Table II) indicate that v (N-H) of ethylenediamine (en) shift to a lower spectral region while the (N-H) bending mode of the amine splits into two bands, of which one appears in a slightly higher region while the other in a lower spectral region. These observations are similar to those obtained with the complexes of ethylenediamine and some metal halides18 and it may, therefore, be inferred that coordination occurs through the nitrogen atom to titanium.
J. Less-Common
Metals,
17 (1969) 437-441
R. C. PAUL, H. S. MAKHNI,
440 TABLE
P. SINGH, S. L. CHADHA
II
IMPORTANT INFRARED SPECTRALBANDS OF (a) NBZA AND ITS COMPLEXES (b)mxF AND ITS COMPLEXES (C) DMSo AND ITS COMPLEXES (d) PYRIDINE AND ITSCOMPLEXES AND (e) ETHYLENEDIAMINE AND ITS COMPLEXES WITH TiTANIUM(IV) CHLORIDE ALKOXIDES.
NMA TiClz(OMe)a+NMA TiCl~(OPr*)~*NMA TiClz(OBu*)z. NMA TiCl(OC2H&1)3+ NMA
3280 s 3350 s 3320 s 3310 s 3305 s
Compound
Y
DMF TiClz(OMe)z. DMF TiClz(OEt)z.DMF TiClz(OPrn)z. DMF TiClz(OPri)o. DMF TiCle(OBu*)z. DMF TiCle(OBui)z* DMF TiCi(O&H&l)3. DMF
1680 V.S. 1650 V.S. 1650 “.S. 1650 V.S. 1640 V.S. 1645 V.S. 1650 v.s. 1645 V.S.
~ornpo~nd DMSO TiClz(OMe)z - DMSO TiClz(OEt)e+ DMSO TiClz(OPrfi)z. DMSO TiClz(OPr*)g. DMSO TiClz(OBu*)s. DMSO Ti&(OBu‘)2 f DMSO TiCl(OC~H~Cl)~~zDMSO
Cd)
1670 V.S. 1605 V.S. 1620 v.s. 1610 V.S. 1610 V.S.
(C=O)
1580 s 1530 s I.555 s 1550 s 1550 s
1300 s I325 s 1320 s ‘315 s
(C-N)
v (N-C)
(N-G=O)
1255 m I270 s 1265 s 1270 m 1270 s 1265 m 1265 m ‘295 s
Iogo m 1130 m 1125 m 1125 m 1125 s 1125 s rI25 m 1125 s
660 680 680 680 685 685 685 690
v
v
1050
6gos,66os
V.S.
ggo-IO00 v,s. 995 v.s. g8o V.S. 995 v.s. 990 V.S. 995 V.S.
m m m m m m m m
(C-S)
v fS=O)
ggclV.S.
1165 s 1180 s 1175 s 1175 s I’75 s
725 s, 720 s, 720 s, 7,220 s, 720 s, 722 s, 725 s,
680 680 680 680 685 680 675
m m m s m m m
ring
vibrations
-
-.
compound
t- (C_.AT)
PY.
1603, 1572, ‘530 1635, 1605, 1550 1630, 1600, 1550
TiClz(OPr”)z *Py TiClz(OPr*)z. aPy
and
Y
Amine
(CA’)
1005, 600 1030, 625 1025, 620
(8)
__ Compound
Y (N-H)
(N-H)
en.
33503 3280 3230 3210
1600 165ow, r6I0, 1500 1605, 1510
TiClz(OMe)z.aen TiClz(OPr{)z. 2811
bending
REFERENCES I R. C. PAUL, B. R. SREENATHAN 2 R. C. PAUL AND S. L. CHADHA,
AND S. L. CIXADHA,~. frtovg.Nwl.,Chem., S~e~tpo~h~rn. Act&, 23A (1957) 1243, 1249. 3 W. GERRARD, M. F. LAPPERT, H. PYSZORA AND J. W. WALLIS, J. Chem. Sot., 4 N.N. GREENWOOD AND K. WADE,J. Chem.Soc.,(r958) 1667. .I. Less-Common
Metals,
17 (rg6g)
437-441
a8 (1966) (1960)
x22.5.
2144.
COMPLEXES OF Ti(IV)
CHLORIDE ALKOXIDES
WITH
0 AXD N
441
BASES
5 R. C. PAUL, S. L. CHADHA AND S. K. VASISHT, J. Less-Common Metals, 16 (I#&) 6 M. L. LARSON AND F. W. MOORE, J. Inorg. Chew, 5 (1966) 801. K. DEHNICKE AND K. U. MEYER, 2. ANorg. Allgem. Chem., 33I (1964) 121. f: J. ARCHEMBAULT AND R. RIVEST, Ca?-t.J. Ghem., 36 (1958) 1461. 9 J. S. JENXXNGS, W. WARDLAW AND W. J. R. WAY, J. Cinem. SK, (1936) 637. IO H. BURGER, Monatsh. Gem., 94 (1963) 574. II D. C. BRADLEY, D. C. HANCOCK AND W. WARDLAW, J. Chem. SOL, (1952) 2773. I2 R. N. BROWN AND C. WINTEK, J. Chem. Sot., (1903) 734. I3 b1. A. J. JUNGBAUR AND C. CURRAN, iVature, 202 (1962) 290.
288.
I4 F. A. COTTON, R. J. FRANCIS AND W. D. HORROCKS, JR., f. Phys. Chem., 64 (1960) Ij34. II. H. NUTTALL, D. E. SCAIFE AND D. W. A. SHARP, J. Inorg. Nucl. Chem., 18 I5 N. S. GILL, (1961) 79. J. Chem. Sot., (1960) 1130. 16 N. N. GREENWOOD AND K. WADE, 17 R. C. PAUL AND S. L. CHADHA, Spectrocltim. A& zz (1966) 615; Id. J. Chem., 6 (1968) 272. Compounds, Wiley, New York, 18 K. NAKAMOTO, Infrared Spectra of Inorganic a4 Coo&nation 1963, p. 187.
J. ~ess-co~~rno~z &!etals, 17 (I&g)
437-441
COMPLEXES OF TITANIUM(IV) CHLORIDE OXYGEN AND NITROGEN BASES
Ii. C. PAUL,
H. S. MAKHNI,
P. SINGH
AND
ALKOXIDES
137
WITH
S. L. CHADHA
Department of Chemistry, Panjab University. Chandigavh-Iq (India) (Received
October z8th, 1968; revised December
Ioth, 1968)
SUMMARY
Solid coordination complexes of titanium(IV) chloride alkoxides with dimethylsulfoxide, dimethylformamide, N-methylacetamide, pyridine, and ethylenediamine have been prepared. Infrared spectra of these complexes indicate that the oxygen and nitrogen atoms, of the sulphoxide and amides, and the nitrogen bases, respectively, coordinate to titanium.
INTRODUCTIOE
Amides, sulfoxides and nitrogen bases are known to form addition compounds with a number of metal halide+-4, and oxyhalide+7. Infrared spectra of a few of these indicate the coordination of the oxygen atoms of the ligands to the metal atoms.-a. Complexes of titanium(IV) chloride have also been reported with amidess. Addition compounds of titanium(IV) chloride alkoxides with donors have not been reported except with alcohols9 and a I : I compound of titanium(IV) chloride triethoxide with dimethylsulfoxidelo. The present communication describes the preparation and study of the infra-red spectra of complexes of titanium(IV) chloride alkoxides, TiClz(OR)z, [R=Me, Et, Pm, Pri, Bu 12,Buil and of titanium monochloride tris(z-chloroethoxide) with some oxygen and nitrogen bases. EXPERIMENTAL
Benzene, ether, dimethylsulfoxide, dimethylformamide, N-methylacetamide, pyridine, ethylenediamine and alcohols were purified by standard methods. Titanium(IV) chloride alkoxides were prepared as described in the literatureg. Preparation of complexes To a solution of the alkoxide in benzene, an equimolar proportion of the ligand in the same solvent was added. Usually, a viscous layer separated out which was washed with benzene and subsequently subjected to reduced pressure. The product was then treated with dry ether when a crystalline compound was obtained. This was repeatedly washed with ether and dried under vacuum. .I. Less-Common Metals, 17 (1969) 437-441
R. C. PAUL, H. S. MAKHNI, P. SINGH, S. L. CHADHA
438
Titanium was determined as described by BRADLEY et al.11 and the chloride content was obtained following fusion with sodium carbonate and potassium hydroxide, silver chloride being precipitated from a nitric acid solution of the cooled melt. Infrared spectra of the complexes were examined as nujol mull films using a Perkin Elmer-337 infrared spectrophotometer. RESULTS AND DISCUSSION Titanium(IV)
chloride
Bu”), and titanium
alkoxide
monochloride
(DMSO), dimethylformamide ethylenediamine (en) with
assigned
By analogy
a hexa
(R=Me,
most form
with
coordination
these,
Et,
react
(DMF), N-methylacetamide the formation of solid addition
results (Table I) indicate that Titanium(IV) chloride alkoxides are dimericls.
TiCls(OR)s
tris(z-chloroethoxide),
titanium them
in the
Pr”, Bun,
and
(NMA), pyridine (Py) and compounds. The analytical
of the complexes have I : I addition compounds
by assuming
Pm,
with dimethylsulfoxide
a I: I stoichiometry. with alcohols9 which
present
to be dimeric.
complexes Cryoscopic
may
be
measure-
TABLE I cCILOURAND NMA
AND
ANALYTICAL
PYRIDINE
AND
DATA
OF THE
Compound
TiClz(OMe)s. DMSO TiClz(OMe)s.DMF TiClz(OMe)z.NMA TiClz(OMe)z+ zen TiClz(OEt)z. DMSO TiClz(OEt)za DMF TiClz(OPr‘)z. DMSO TiClz(OPr’)s. DMF TiClz(OPr”) 2. NMA TiClz(OPr”)z.Py TiClz(OPr’) . en TiClz(OPrn)z. DMSO TiClz(OPrn)z. DMF TiClt(OPrn)2. zPy TiClz(OBu‘)z. DMSO TiClz(OBu’)x. DMF TiCls(OBu’)z. NMA TiClz(OBun)z. DMSO TiClz(OBun)s. DMF TiCl(OC%H&l)3. DMF TiCl(OCsH4Cl)s. NMA TiCl(OCzH&l)z. en
~eSS-COM9aOW
ibfetak,
OF TITANIUM
ALKOXIDE
WITH
DMSO,
DMF,
Found
(%)
Colour and
Required
state
Ti
Cl
Ti
Cl
Yellow viscous Yellow powder Yellow viscous Yellow solid White crystals Yellowish-white crystals White solid Yellow powder Yellow powder Yellowish powder White White crystals Yellowish-white crystals White solid White solid Yellowish-white solid Yellow crystals White solid White solid Yellowish solid Yellowish solid White powder
18.53 18.92 18.92 16.92 16.72 17.02
27.42 27.96 27.96 23.60
18.26
27.35
18.73
27.89
* All the complexes decompose J.
COMPLEXES*
ETHYLENEDIAMINE
17
(1969)
18.86
27.48
16.85
23.25
24.74 25.19
16.23
24.83
16.92
24.98
15.24 15.48 15.48 15.17
22.24 22.91
15.13
22.42
15.37
22.83
22.91
‘5.40
22.79
22.48
15.18
22.38
16.14
23.92 22.54
16.25
23.52
15.21
22.31
22.91
15.36
22.81
17.9 20.70
II.95
17.62
X4.00
13.88
20.62
14.20
21.01
14.12
20.89
14.20
21.01
14.25
20.91
14.00
20.70
14.13
20.62
14.20
21.01
14.17
21.21
12.15
35.95 35.95 37.43
12.01
35.87
12.31
35.68
12.68
36.82
15.24 15.48 12.13
12.15 12.63
before reaching their melting points. 437-441
(%)
COMPLEXES
OF Ti(IV)
CHLORIDE
0 ANI) N BASES
ALKOXIDESWITH
439
ments for the determination of the molecularity of these complexes could not be carried out on account of their insolubility in common organic solvents. The I: I complexes, therefore, may be tentatively represented as donor 7 \ R_.~lTiJ”\Ti c,’
CZ-R ‘Of k
‘Cl i donor
Infrared spectra have been recorded from 4000 to 600 cm-l, the important bands are given in Table II. The N-H stretching band of pure NMA at 3280 cm-l moves to a higher spectral region in its complexes with titanium(IV) chloride alkoxides. The trend of the shift is in line with the corresponding shift discussed in the complexes of NMA with metal halides3, and oxyhalides5, which suggests that the nitrogen atom of this amide is not the donor. NMA and DMF exhibit the amide-I band at 1650-1680 cm-1 while the amideII band of NMA is present at 1550 cm-l. These bands shift to a lower spectral region in the complexes of these amides; this shift establishes that the carbonyl oxygen coordinates to titanium(W) chloride alkoxides and it is in agreement with the observations made regarding the complexes of amides with metal halides’-33”. The spectral bands of the amides in the 1100-1300 cm-1 region assigned to the vibrations of the C-N group, shift to a higher spectral region in the complexes; this also supports coordination by the carbonyl oxygen of the amide. DMF has a spectral band at 655 cm-l, due to the N-C=0 bending frequency. This band shifts to the higher spectral region at 680 cm-l, which is in agreement with the observations made by JUNGBAUR A~W CURRANTS. Y (S =0) of pure DMSO, present at 1050 cm-l, shifts to a lower spectral region by 40-60 cm-l in the spectra of the complexes of DMSO with titanium(W) chloride alkoxides. This indicates the coordination of DMSO through its oxygen atom and is in agreement with the observation by COTTOY et ~1.14.The Y (C-S) of DMSO, lying at 660 cm-1 and 690 cm- 1, shift to a higher spectral region in the spectra of its complexes which further confirms the coordination of DMSO through the oxygen atom. Comparison of the significant infra-red spectral bands of pyridine and its complexes with titanium(IV) chloride alkoxide (Table II) indicates that the bands due to C-C and C-N stretching frequencies shift to a higher spectral region. The ring vibrational bands of pyridine at 1005 cm-1 and 600 cm-l shift to 1025 and 625 cm-l,
respectively.
These
observations
may
be interpreted
in terms
of the
pyridine nitrogen acting as the donor, and they are in agreement with the observations by GILL et a1.15, GREENWooD AND WADERS and PAUL AND CHADHA~~. The spectra of the complexes (Table II) indicate that v (N-H) of ethylenediamine (en) shift to a lower spectral region while the (N-H) bending mode of the amine splits into two bands, of which one appears in a slightly higher region while the other in a lower spectral region. These observations are similar to those obtained with the complexes of ethylenediamine and some metal halides18 and it may, therefore, be inferred that coordination occurs through the nitrogen atom to titanium.
J. Less-Common
Metals,
17 (1969) 437-441
R. C. PAUL, H. S. MAKHNI,
440 TABLE
P. SINGH, S. L. CHADHA
II
IMPORTANT INFRARED SPECTRALBANDS OF (a) NBZA AND ITS COMPLEXES (b)mxF AND ITS COMPLEXES (C) DMSo AND ITS COMPLEXES (d) PYRIDINE AND ITSCOMPLEXES AND (e) ETHYLENEDIAMINE AND ITS COMPLEXES WITH TiTANIUM(IV) CHLORIDE ALKOXIDES.
NMA TiClz(OMe)a+NMA TiCl~(OPr*)~*NMA TiClz(OBu*)z. NMA TiCl(OC2H&1)3+ NMA
3280 s 3350 s 3320 s 3310 s 3305 s
Compound
Y
DMF TiClz(OMe)z. DMF TiClz(OEt)z.DMF TiClz(OPrn)z. DMF TiClz(OPri)o. DMF TiCle(OBu*)z. DMF TiCle(OBui)z* DMF TiCi(O&H&l)3. DMF
1680 V.S. 1650 V.S. 1650 “.S. 1650 V.S. 1640 V.S. 1645 V.S. 1650 v.s. 1645 V.S.
~ornpo~nd DMSO TiClz(OMe)z - DMSO TiClz(OEt)e+ DMSO TiClz(OPrfi)z. DMSO TiClz(OPr*)g. DMSO TiClz(OBu*)s. DMSO Ti&(OBu‘)2 f DMSO TiCl(OC~H~Cl)~~zDMSO
Cd)
1670 V.S. 1605 V.S. 1620 v.s. 1610 V.S. 1610 V.S.
(C=O)
1580 s 1530 s I.555 s 1550 s 1550 s
1300 s I325 s 1320 s ‘315 s
(C-N)
v (N-C)
(N-G=O)
1255 m I270 s 1265 s 1270 m 1270 s 1265 m 1265 m ‘295 s
Iogo m 1130 m 1125 m 1125 m 1125 s 1125 s rI25 m 1125 s
660 680 680 680 685 685 685 690
v
v
1050
6gos,66os
V.S.
ggo-IO00 v,s. 995 v.s. g8o V.S. 995 v.s. 990 V.S. 995 V.S.
m m m m m m m m
(C-S)
v fS=O)
ggclV.S.
1165 s 1180 s 1175 s 1175 s I’75 s
725 s, 720 s, 720 s, 7,220 s, 720 s, 722 s, 725 s,
680 680 680 680 685 680 675
m m m s m m m
ring
vibrations
-
-.
compound
t- (C_.AT)
PY.
1603, 1572, ‘530 1635, 1605, 1550 1630, 1600, 1550
TiClz(OPr”)z *Py TiClz(OPr*)z. aPy
and
Y
Amine
(CA’)
1005, 600 1030, 625 1025, 620
(8)
__ Compound
Y (N-H)
(N-H)
en.
33503 3280 3230 3210
1600 165ow, r6I0, 1500 1605, 1510
TiClz(OMe)z.aen TiClz(OPr{)z. 2811
bending
REFERENCES I R. C. PAUL, B. R. SREENATHAN 2 R. C. PAUL AND S. L. CHADHA,
AND S. L. CIXADHA,~. frtovg.Nwl.,Chem., S~e~tpo~h~rn. Act&, 23A (1957) 1243, 1249. 3 W. GERRARD, M. F. LAPPERT, H. PYSZORA AND J. W. WALLIS, J. Chem. Sot., 4 N.N. GREENWOOD AND K. WADE,J. Chem.Soc.,(r958) 1667. .I. Less-Common
Metals,
17 (rg6g)
437-441
a8 (1966) (1960)
x22.5.
2144.
COMPLEXES OF Ti(IV)
CHLORIDE ALKOXIDES
WITH
0 AXD N
441
BASES
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