See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/232262278

ORGANIC COMPO~JNDS OF NIOBIUM AND TANTALUM

IV. REACTIONS OF NIOBIUM AND TANTALUM
PENTAETHOXIDES WITH /V&DIKETONES

Article · January 1965

CITATIONS READS

0 27

2 authors, including:

Pramesh N Kapoor
University of Delhi
129 PUBLICATIONS   2,232 CITATIONS   

SEE PROFILE

All content following this page was uploaded by Pramesh N Kapoor on 28 May 2014.

The user has requested enhancement of the downloaded file.

JOURNALOF THE LESS-COMMON
METALS 339

ORGANIC COMPO~JNDS OF NIOBIUM AND TANTALUM

IV. REACTIONS OF NIOBIUM AND TANTALUM PENTAETHOXIDES WITH

/V&DIKETONES

P. N. KAPOOR AND R. C. MEHROTRA

Chemistry Department, Rajastkan Unziversity, Jaipuv (India)
(Received January Izth, 1965)

SUMMARY

The reactions of niobium pentaethoxide with acetylacetone, benzoylacetone

and of tantalum pentaethoxide with acetylacetone have been studied and derivatives
of the type M(OEt)~(lig)~-~ (where M = Nb or Ta; lig = acetylacetone or benzoyl-
acetone; x = 4,3 or 2) have been isolated. These derivatives interchange their ethoxy
groups with tertiary butoxy groups on refluxing with tert.-butyl alcohol. The molecular
weights of p-diketonate as well as /?-ketoester derivatives of niobium and tantalum
have been determined ebullioscopically in benzene.

INTRODUCTION

FUNKI isolated the dichloride dialkoxy acetylacetonates of niobium and tan-

talum by the reaction of their corresponding yentachlorides with acetylacetone in the
presence of alcohol. Recently, a physicochemical study of the derivatives of niobium
and tantalum of the type XsM (OIQAcac (X = chloride or bromide) was carried out
by DJORDJEVIC ANDKATOVIC~.Much work has also been already carried out on the
reactions of alkoxides of aluminiuma, titanium*, germaniums, lanthanum, neo-
dymiumj, praseodymium7, tantalum8 and vanadium9 with @-diketones. It was
therefore considered of interest to study similar reactions of niobium and tantalum
pentaethoxide with ,8-diketones.
The reactions of niobium and tantalum pentaethoxide with ,&diketones
(acetylacetone and benzoylacetone) have now been carried out in different molar
ratios and mono-, di- and tri-substituted products of the type M(OEt).(li&-,
(where M = niobium or tantalum and lig = acetylacetone or benzoylacetone and
x == 4, 3 or 2) have been isolated in almost quantitative yields. Similar results were
obtained by BRADLEY ANDWHITLEY~ who studied the reactions of tantalum penta-
ethoxide with benzoylacetone and also obtained the trisubstituted derivative as the
ultimate product. The failure to prepare tetra- and penta-subsituted derivatives of
these metals by refluxing the corresponding pentaethoxides with excess of ligand
(I : > 5) for several hours could be ascribed10 either due to steric hindrance or a satu-
rated coordination state of the metal in compound (III).
The experimental technique was the same as described earlierlo. The following

J. Less-Common &f&a&, 8 (1965) 339-346

340 P. N. KAPOOR,R. C. MEHROTRA

plausible structures can be ascribed to the various new compounds isolated during
the present investigations :

\ CM3 R/ (OR)3
\
CH3
)=J
I\ \o-cN\
(I) (II) R’ 1 P CH3

kc\ 81, C
CH 3

(!II>
(W i n,ob,um or tantalum, OR= OEt or OBu’; R’= -CH3 or -C6H5)

All the above derivatives are dark brown viscous liquids, highly susceptible to
moisture, and soluble in benzene. On heating under reduced pressure, only the tetra-
ethoxymono$-diketonate derivatives could be distilled unchanged; the di- and tri-
substituted derivatives decomposed.
The reactions of niobium and tantalum pentaethoxides with excess (5 moles)
of acetylacetone at room temperature yielded a tetraethoxymonoacetylacetonate
which was found to be monomeric having therefore a coordination number of six. The
reactions of niobium and tantalum pentachlo~des with alcoholsrr gave the tri-
substituted products:
MC15+ 3 ROH __ M(OR)aC& + 3 HCI
FUNKI studied similar reactions in presence of acetylacetone, and obtained dichloro-
dialkoxo-acetylacetonates, indicating that a coordination number of six is the most
common and stable for niobium and tantalum:
MCI5 + z ROH + HAcac - MCla (0R)zAcac + 3 HCl
A comparison of the boiling points of these alkoxide @diketone derivatives, as
well as of the fi-ketoesters derivatives10 of niobium and tantalum shows that the
tantalum derivatives are more volatile than the corresponding niobium derivatives.
This is in agreement with the observations of BRADLEY, CHAKRAVARTY ANDWARD-
LAW~Zwho have shown that normal alkoxides of tantalum are more volatile than the
corresponding alkoxides of niobium (Table I).
Further alcoholysis reactions of mono-, di- and tri-acetylacetonate of niobium
and tantalum with &rt.-butyl alcohol in the presence of benzene provided a convenient
method for the preparation of the corresponding tertiary butoxide derivatives. These
reactions were comparatively more facile in case of tantalum :
(EtO)sM (lig)s+ + ButOH - (Bu~O)~M (lig)s-, + x EtOH
(excess)
(where M = Nb or Ta; lig = acetylacetone; x = 4, 3 or 2).
The tert.-butoxide derivatives thus formed are white or light yellow solids which
can be purified by sublimation under reduced pressure.
The molecular weights of a few typical derivatives were determined ebullios-
topically in benzene and found to be monomeric.

J. Less-Common Metals, 8 (1965) 339-346

ORGANIC COMPOUNDS OF NIOBIUM AND TANTALUM. IV 341

TABLE I
BOILING POINTS AND MOLECULAR WEIGHTS

Compounds Niobium T~~ta~~~

___._.~ __..._-
b.p.(°C/mnz) Mol. wt. Mol. wt. b.p.(°C/mm) Mol. wt. MOE. wt.
average talc. average talc.
fOtWZd found
.. _ _-. ~~_.~~_. _
M (OEt)4(Acac) I rg/o.8 372 372 112jO.8 5x0 460
M (OEt)b (Bzac) 135-140/0.2 454 434
M (OEt)d (Meacac) 127j0.8 403 388 11010.5 493 476
M (OEt)a (Meacac)z rzr/o.G 497 458 123b.9 511 546
M @Et)2 (Meacac)z 123io.i’ r18jo.6
M (OEt)d (Etacac) 113f0.2 428 402 108/0.2 5x4 490
M @Et)3 (Etacac)z I I9fO.25 525 486 ‘34/‘.0 576 574
M (0Et)z (Etacacjs ‘35/0.4 12610.9
M (OBut)4 (Acac) 70-80/0.5* g*100/1.5*
M (C)But)3 (Acac)z go-100/2.0* 528 510 85-9511 .o*
M (C)But)2 (Acac)a 8o-go/o.8* 550 536
M (OBu”)4(Bzac) ISO-140/0.2* 558 540
M (OBut)a (Meacac) IIo--I20/0.2* 6x9 588
M (0But)~ (Meacac)z 95-I 15/o.7* 635 630
M (OBut)4 (Etacac) 105-I 15/o-4* 603 602

M (0Bz.x”)~(Etacac)z IID-120/1.0*

* Sublimation at bath temperature.

Acac, Acetylacetone; Bzac, Benzoylacetone; Meacac, Methylacetoacetate; Etacac, Ethylaceto-
acetate.

EXPERIMENTAL

Niobium and tantalum pentaethoxides were prepared by the ammonia meth-

odl2,la. Acetylacetone was dried by refluxing over aluminium isopropoxide and puri-
fied by fractionation. Benzoylacetone was distilled under reduced pressure. tert.-Butyl
alcohol was distilled over freshly ignited quick-lime and was fractionated over sodium
tert.-butoxide. Benzene (B.D.H.) was dried over sodium wire followed by azeotropic
fractionation in the presence of ethanol.
Throughout, all-glass apparatus with interchangeable joints was used. Extreme
care was taken to exclude moisture from the system. Fractionations were carried out
in a column packed with Raschig rings. Molecular weights were determined in a
semimicro ebulliometer (Gallenkamp) using a thermistor sensing.
Niobium and tantalum were estimated as niobium and tantalum pentaoxides
by direct ignition of the compounds after digestion with ammonia and nitric acid in
a platinum crucible. Ethanol was estimated by oxidation with normal dichromate in
12.5% sulphuric acidl4.

REACTIONS

Reaction of niobium #entaethoxide with acetylacetone in molar ratio of I: excess in cold

Acetylacetone (5.88g) was added to niobium pentaethoxide (1.88 g) in benzene
(5.0 g), when an exothermic reaction took place and the colour of the solution became

J. LEss-CB~~on Metals, 8 (1965) 339-346

342 P. N. KAPOOR, R. C. MEHROTRA

yellow. The solution was left overnight and the solvent removed under reduced
pressure (0.5 mm) at room temperature for eight hours. An orange-yellow liquid
(2.30 g) remained which was distilled under reduced pressure 114’/0.5 mm. Niobium,
24.60; Nb (0Et)JAcac requires Nb, 24.90.

Reaction of tantalum pentaethoxide with acetylacetone in molar ratio of I : I in benzene

Acetylacetone (0.73 g) was added to a benzene (50 g) solution of tantalum
pentaethoxide (2.96 g). The reaction was slightly exothermic and the solution turned
yellow. The solution was refluxed under a fractionating column and the binary
azeotrope of ethanol-benzene collected at 68-80°C. The total refluxing was carried out
for about 6 h. The excess of the solvent was then distilled off at a high reflux ratio. A
yellow solution was obtained which was evaporated under reduced pressure (0.05 mm)
at room temperature. An orange-yellow liquid (3.34 g) remained which was distilled
under reduced pressure 10610.4 mm at 140~-5o’C. On standing, this liquid solidified
to an orange-yellow solid.
Found: ethanol in azeotrope, 0.32 g; replacement of one mole requires 0.33 g.
Ta, 39.32%; ethoxy, 40.47%. Ta(OEt)d(AcAc) requires Ta, 39.30%; ethoxy, 39.17%.

Reaction of niobium pentaethoxide with acetylacetone in molar ratio of I : 5 in benzene

Acetylacetone (3.05 g) was added to niobium pentaethoxide (I.94 g) in a
reaction flask. An exothermic reaction took place and the solution turned yellow.
Benzene (60 g) was then added and the mixture refluxed under a fractionating column.
The binary azeotrope of ethanol benzene was collected from 68-80°C. The reflux of
the reaction mixture was continued and the azeotrope was collected slowly; excess of
benzene was then distilled out at high reflux ratio. The total time of reflux was about
8 h. A clear brown solution was obtained which was dried under reduced pressure
(0.6 mm), at bath temperature of 60-70°C. A dark brown viscous pasty solid (2.94 g)
was obtained. Unsuccessful attempts were made to distil this compound under reduc-
ed pressure ; some orange-yellow vapours were evolved as a result of probable de-
composition.
Found: alcohol in azeotrope, 0.99 g; replacement of three moles requires 0.84 g.
Nb, 20.10%, Nb (0Et)z (AcAc)a requires Nb, 19.34:/o.

Reaction between niobitim tetraethoxymonobenzoylacetonate with tert.-butyl alcohol

Tert.-butyl alcohol (3.0 g) was added to a solution of niobium tetraethoxy-
monobenzoylacetonate (1.0 g) in benzene (50 g). The colour of the solution became
orange-yellow. The reaction mixture was refluxed under a column for 18 h and the
azeotrope was collected slowly.
Excess solvent was distilled out under reduced pressure. An orange-yellow
solid (1.26 g) which could be sublimed unchanged under reduced pressure at a temper-
ature of 13o-14o’C/o.3 mm. ; 0.85 g was obtained in this way.
Fozcnd: ethanol in azeotrope, 0.44 g; replacement of 4 moles requires 0.42 g.
Nb, 17.10%; Nb (OBut)J(Bzac) requires Nb, 16.93%.
The results obtained from the reactions of niobium and tantalum penta-
ethoxides with acetylacetone and with benzoylacetone, and those from the reactions
are given in Tables II and III respectively, and those from the reactions between the
above derivatives and tert.-butyl alcohol are summarised in Table IV.

J. Less-Common Metals, 8 (1965) 339-346

 TABLE II
REACTIONS OF NIOBIUM AND TANTALUM PENTAETHOXIDES WITH ACETYLACETONE

Alkoxide Acetyl- Product and state .4mount of alcohol b.p. Analysis

(K) acetone in azeotrope I”Clmm)
Metal Alkoxy
(gl
Found Calc.
Found CdC. Found Calc.
(gl ld
(%) (%I (%) (%)
I :I Nb (OEt)h 0.48 Nb (0Et)r (Acac) orange 0.19 0.22 I rg/o.8 25.20 24.95 44.40 48.42
(1.51) yellow low melting solid (I mole)
(1.82 g)
112 Nb (0Et)s 1.31 Nb (0Et)s (Acac)z 0.61 0.60 Few drops 22.4r 21.80 32.26 31.73
(2.07) brown viscous liquid (2 moles) of liquid
(2.7 g) obtained at
105/0.8; Nb,
16.0%
I :3 Nb (0Et)s 1.63 Nb (0Et)z (Acac)s red- 0.74 0.75 Decomposed 20.07 18.76
19.34 18.73
(1.73) brown viscous liquid (3 moles)
(2.60 g)
Nb (0Et)a 3.05 Nb (0Et)z (Acac)s red- o.99* 0.84 Decomposed 20.10 ‘9.34
(1.94) brown pasty solid (3 moles)
(2.94 g)
Ta (0Et)s 0.73 Ta (0Et)r (Acac) orange- 0.32 0.33 10610.4 39.32 39.30 40.47 39.17
(2.96) yellow low melting solid (I mole)
(3.34 g)
Ta (0Et)s 0.76 Ta (0Et)s (Acac)z 0.34 0.35 Decomposed 36.51 35.18 26.53 26.28
(1.54) brown viscous liquid (2 moles)
(1.89 g)
Ta (0Et)j 1.72 Ta (0Et)z (Acac)a 0.77 0.79 Decomposed 32.68 31.84 16.08 15.85
(2.33) brown viscous liquid (3 moles)
(2.8 g)
Ta (0Et)s 2.69 Ta (0Et)z (Acac)s 0.86* 0.74 Decomposed 33.55 31.84
(2.18) brown pasty solid (3 moles)
(2.96 g)

* The higher values of alcohol in the azeotrope from the reactions of niobium and tantalum pentaethoxide with excess of p-diketones might be due to
.. ,*n.... . . . . ,. . . . ..
a Small amOUnt of p-CIlKCtOUeS DelUg CarrlCCI Out along with alcohol-benzene azeotrope.
i’ L
TABLE III
REACTIONS OF NIOBIUM PENTAETHOXIDES WITH BENZOYLACETONE

Benzoyl- Product ami state Amount of alcohol Analysis

acetone in azeotrope ;&mm] p--
Metal Alkoxy
(sl -p
Fowzd Catc.
Found CaEc. -. Found Calc.
fsl (g)
VU (%.I C%) (%I
--~_-- ~----_.-._ ~____ --- --
I :I Nb (0Et)a 0.92 Nb (0Et)d (Bzac) 0.26 0.26 125-135/0.2 21.30 21.38 43.0 41.48
(1.8I) red viscous liquid (I mole)

(2.43 91
2 Nb (0Et)s 1.93 Nb (OEt)s (Bzac)z 0.56 0.54 Decomposed 16.82 16‘87 23.30 24.55
(r.86) red viscous liquid (2 moles)
(3.19 g)
3 Nb (0Et)s 2.14 Nb (0Et)z (Bzac)a 0.57 0.60 Decomposed 14.16 13.93 12.13 13~52
(1.40) red viscous liquid (3 moles)
(2.93 g)
6 Nb (0Et)s 4.85 Nb (0Et)Z (Bzac)a 0.84* OhQ Decomposed 14.11 13.93
(1.58) red viscous liquid (3 moles)
(3.13 8)

Reactions of niobium and tantalum pentaethoxides with acetyhcetone in molar ratio of I : excess at room temperature
1:10 Nb (0Et)B 5.88 Nb (OEt)s (Acac) At room temperature 114io.5 24.60 24.90
(r.88) orange-yellow liquid
(2.3 g)
I :10 Ta (0Et)s 3.40 Ta (OEt)d (Acac) At room temperature rob/o.4 39.44 39.30
(1.38) orange-yellow liquid
(1.56 g)
TABLE 1V
INTERCHANGE WITH t&.-BUTYL ALCOHOL

tert. Product and state A mount of alcohol Sublimation Analysis of the metal
ButyE ir&azeotrope at bath ~._
alcohol temperature Found Calc.
&und Calc.- (gl (Sl
(69 (“ClmW
(s/ (CC)
-~-- _“~_
Nb @Et)4 (Acac) 4.0 Nb (OBu$ (Acac) 0.2 0.22 70-8510.5 19.81 lg.18
(0.45) orange-yellow solid (4 moles)
Nb (OEt)a(Acac)z 9.93 Nb (OBu’)s (Acac)z 0.65 0.66 90-IOO/2.0 18.91 18.20
(2.03) yellow-solid (3 moles)
Nb(OEt)s (Acac)g 7.00 Nb (O&I’)* (Acac)a 0.31 0.32 8o-go/o.8 18.08 17.32
(1.66) brown solid (2 moles)
Nb fOEt)r (Bzac) 3.00 Nb (OBu$ (Bzac) 0.44 0.42 ISO-140/0.3 17.10 16.93
(I.01 orange-yellow solid (4 moles)
Ta (0Et)r (Acac) 4.50 Ta (OBut)d (Acac) 0.42 0.4I go-roo/r.g 32.37 31.60
(I .o3) light yellow solid (4 moles)
Ta (OEt)j (Acacjz g.00 Ta (OBu”)a (Acac)s 0.27 0.27 85-9511.0 30.92 30.24
(1.00) yellow solid (3 motes)
 P. N. KAPOOR, R. C. MEHROTRA
346

ACKNOWLEDGEMENT

One of the authors (P.N.K.) is grateful to the Council of Scientific and Industrial
Research, New Delhi, for the award of a Junior Research Fellowship.

REFERENCES

I H. FUNK, Ber., 67B (1934) 1801.

2 Nucl.Chem., 25 (1963) Iogg.
C. DJORDJEVICAND V. KATOVIC,J.Inorg.
3 R. K. MEHROTRA AND R.C.MEHROTRA,CU~.J. Chem., 3g (1961) 795.
4 K.C. PANDE AND R. C.MEHROTRA,C~~~. Ind., (1958) 1198.
5 G. CHANDRA, Ph.D. Thesis, RajasthanUniversity, Jaipur,1963.
6 T. N. MISRA,Ph.D. Thesis, RajasthanUniversity, Jaipur.1963.
7 S. N. MISRA,Ph.D. Thesis, RajasthanUniversity, Jaipur,1964.
8 D. C. BRADLEY, Progr. Inorg. Chem., z (1960) 320.
g R. K. MITTAL,Ph.D. Thesis, RajasthanUniversity, Jaipur,1963.
IO R. C. MEHROTRA AND P.N. KAPOOR,J. Less-Common Metals, 7 (1964) 176, 453.
II H. FUNK AND K.NIEDERLANDER, Ber., 62B (1929)1688.
12 D. C. BRADLEY, B.N.CHAKRAVARTI AND W. WARDLAW,J. Chem.Soc.. (1956) 2381.
13 D.C. BRADLEY, W. WARDLAW AND A. WHITLEY,J. Chem..Soc.,(1955),
726.
14 D. C. BRADLEY AND W. WARDLAW,J. Chem. Sot., (1950) 3450.

J. Less-Common Metals, 8 (1965) 339-346

View publication stats