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Cjbas 13 01 01 01
Cjbas 13 01 01 01
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Abstract
Titanium (IV)
The reaction of TiF4 with salts (C2H5)4NF, (CH3)4NCl and (C4H9)4NBr, in anhydrous
CH3CN produced complexes [TiF4X]- (X=F-,Cl-,Br-). These were characterized by
elemental analysis, IR, UV/Visible and 81Br NMR spectroscopy. In this paper, the
optimized geometries and frequencies of the stationary point and the minimum-energy
paths are calculated at the B3LYP/6-311G (d,p) level of theory too. Theoretical results
showed that the Ti-X (X= F, Cl, Br) bond length values for the [TiF4X]- in compounds
1-3 are 1.863, 2.453 and 2.610 respectively. On the other hand the Ti-F bond length
values in [TiF4X]- are 1.863, 1.838 and 1.837 , respectively. These results reveal that
the bond order for Ti-X bonds decrease from compounds 1 to 3, while for Ti-F bonds,
the bond orders increase. These results reveal that the bond order for Ti-X bonds
decrease from compounds 1 to 3, while for Ti-F bonds, the bond orders increase. It can
be concluded that the decrease of Ti-X bonds lengths and the increase of Ti-F5 bond
lengths in compounds 1-3 result from the increase of the hyperconjugation from
compounds 1 to 3. Harmonic vibrational frequencies and infrared intensities forTiF5,
TiF4Cl and TiF4Br are studied by means of theoretical and experimental methods.
The calculated frequencies are in reasonable agreement with the experimental values.
fluorides, Synthesis
ab initio calculations
density functional
calculations
Vibrational analysis
B3LYP level
1.Introduction
Properties and applications of technologically important inorganic compounds of titanium are surveyed.
Raw materials and pigment production processes are reviewed. Mixed oxides, e.g., barium titanate, and
halides of titanium are important raw materials for electroceramics. Titanium tetafluoride and its derivatives
have applications in fluorohydrins; addition of carbanions to aldehydes and imines, chemoselective
synthesis and deprotection of geminaldiacetates of aldehydes. Titanium tetrafluoride and Lewis bases L
normally form 1:2 adducts TiF4L2 [1]. TiF4 is stable in water and even in basic
a)
b)
c)
Figure 1. Optimized geometries of (a) [TiF5]-, (b) [TiF4Cl]- and (c) [TiF4Br]at B3LYP/6-311G(d,p) level of theory.
[TiF5]
[TiF4Cl]-
[TiF4Br]-
1.8265
1.8271
1.8263
1.8637
1.8637
1.8092
1.8072
1.8087
1.8389
2.4536
1.8077
1.8073
1.8085
1.8374
2.6107
F2-Ti1-F3
F2-Ti1-F4
F2-Ti1-F5
119.9
120
90
120.1
119.9
90.78
119.7
120
91
F2-Ti1-X6
90
89.1
89
Bond lengths ()
Ti1-F2
Ti1-F3
Ti1-F4
Ti1-F5
Ti1-X6
Bond angles ()
B3LYP/6-311G(d,p)
[TiF5][TiF4Cl][TiF4Br]-
Exptl
571, 649,793
566, 625
551, 637
2.2. Synthesis of
Tetraethylammoniumpantafluorotitanate
(IV),[(C2H5)4N][TiF5] (1)
To a solution of TiF4 (0.22 g, 1.77 mmol) in
MeCN, the solid powder tetraethtylammonium
fluoride (0.30 g, 2.01mmol) was added under
stirring at room temperature until a white solid
precipitate was formed. After 2 hours stirring, the
2.3.
Synthesis
of
Tetrametyl
ammoniumhalotetrafluorotitanate
(IV),
[(CH3)4N][TiF4Cl] (2)
The preparation is like as pervious method: A
solution of TiF4 (0.26 g,2.09 mmol) in MeCN the
solid powder tetrametylammonium chloride (0.25
g, 2.28 mmol) was added under stirring at room
temperature until white off solid precipitate was
formed. After 2 hours stirring, the mixture was
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
200 250 300 350 400 450 500 550 600 650 700 750 800
Vibration
(C4H9)4N
Intensity
( cm-1)
Vibration
Intensity
1473
15,CH2,asym.def
(ms)
3383
CH2+19
(m, br)
1384
16,CH2, sym.str
(s)
3315
CH2+8
(w, br)
1168
rock,CH2,roking 14
(m)
3225
CH2, asym.str
(sh)
1062
18, C4asym.str
(ms)
3010
13,CH2, asym.str
(w,br)
463
19, C4,dif.
(w,br)
2962
14,asym.str
(w,br)
453
19, C4,dif.
(w,br)
2877
14,CH2, asym.str
(w,br)
2765
7+ 16
(w)
637
Ti -F
(vs)
2396
3+ 8+ 16
(w)
551
Ti-F
(vs)
2085
8+ 15
(w,br)
393
Ti- Br
(m)
[TiF4Br]-
ammonium
(2)
2.3.
Synthesis
of
Tetrametyl
formed.
1
(,M-1cm-1)
2
(,M-1cm-1)
279(429)
382(55)
682(18)
250
300
350
400
450
500
Vibration
Intensity
(CH3)4N+
( cm-1)
Vibration
Intensity
1489
15,CH2,asym.def
(ms)
3381
CH2+19
(m, br)
1405
16,CH2, sym.str
(s)
3225
CH2+8
(w, br)
1293
rock,CH2,roking 14
(m)
3017
CH2, asym.str
(sh)
952
18, C4asym.str
(ms)
2980
13,CH2, asym.str
(w,br)
499
19, C4,dif.
(w,br)
2962
14,asym.str
(w,br)
428
19, C4,dif.
(w,br)
2780
14,CH2, asym.str
(w,br)
2655
7+ 16
(w)
637
Ti -F
(vs)
2466
3+ 8+ 16
(w)
551
Ti-F
(vs)
1850
8+ 15
(w,br)
393
Ti- Br
(m)
[TiF4Cl]
(,M-1cm-1)
246)237(
(,M-1cm-1)
282)190(
(,M-1cm-1)
381)108(
( cm )
Vibration
(C2H5)4N
Intensity
( cm-1)
Vibration
Intensity
1492
15,CH2,asym.def
(ms)
3387
CH2+19
(m, br)
1449
16,CH2, sym.str
(s)
3277
CH2+8
(w, br)
1182
rock,CH2,roking 14
(m)
3028
CH2, asym.str
(sh)
1065
18, C4asym.str
(ms)
2995
13,CH2, asym.str
(w,br)
499
19, C4,dif.
(w,br)
2968
14,asym.str
(w,br)
428
19, C4,dif.
(w,br)
2780
14,CH2, asym.str
(w,br)
2655
7+ 16
(w)
783
Ti -F
(vs)
2448
3+ 8+ 16
(w)
649
Ti-F
(vs)
1850
8+ 15
(w,br)
571
Ti- Br
(m)
[TiF5]
1.4
1.2
1
0.8
0.6
0.4
0.2
0
200
250
300
350
400
450
500
(KBr Disk)
1 (,M-1cm-1)
220 (672)
283)327(
4 (,M-1cm-1)
377)128(
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the metallotropic shifts in cyclopentadienyl
(trimethyl)
silane,-germane
andstannane. Journal of Molecular Structure:
THEOCHEM, 763, 21-28 (2006).
DOI: 10.1016/j.theochem.2006.01.011
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GASSIAN 98 (Revision A. 3) Gaussian Inc.,
Pittsburgh, PA, USA, 1998.
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Becke
A.
D.:
Density-functional
thermochemistry. III. The role of exact
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5648-5652 (1993).
DOI: 10.1063/1.464913