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Nitryl Nitrato Complexes of Indium and Thorium.

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Nitryl Nitrato Complexes of Indium and Thorium
The infrared spectra of (6)-(8) and (10) also contain the
bands characteristic of covalently bonded nitrate groups.
By Prof. Dr. M. Schmeisser and Dip].-Chem. G . Kohler
Institut fur Anorganische Chemie und Elektrochemie,
Technische Hochschule Aachen (Germany)
The synthesis of anhydrous nitrates using chlorine nitrate
and chlorides or bromides [I] has been applied to indium
halides. On treatment of InBr3 with excess CIN03 at 2OoC,
a quantitative yield of nitryl tetranitratoindate(lI1) ( I ) was
obtained as a white, readily hydrolysable solid:
2 InBr3
+ 10 CIN03
2 N02[In(N03)4]
-t
+ 3 Br2 + 5 Cl2 + 0 2
Received: March 22nd. 1965
[Z 945/771 I€]
German version: Angew. Chem. 77, 456 (1965)
[ I ] M. Schmeisser and K . Brundle, Angew. Chem. 69, 781 (1957);
cf. C . Brauer: Handbuch der praparativen anorganischen Chemie.
Verlag Enke, Stuttgart 1960, Vol. I , p. 298.
[2] R . A. Marcus and J . M. Fresco, J. chem. Physics 27, 564
(I 957).
[3] D. W. A. Sharp and J. Thorle.v, J. chem. SOC.(London) 1963,
3557.
141 C. C. Addison and E. M. Cotehouse, J. chem. SOC.(London)
1960, 613.
(1)
The structure of the complex is supported by the fact that
equimolar amounts of ( I ) and CsNO3 react together in
anhydrous nitric acid at 20 O C to give a quantitative yield of
white crystals of cesium tetranitratoindate(II1) (2), which is
also very sensitive towards hydrolysis.
NO2fIn(N03)4]
+ CsN03
+ Cs[in(NO3)4] i N2Os
The infrared spectrum of (2) does not contain a band for the
nitryl cation, which occurs at 2360 cm-1 in the spectrum of
( I ) [2], nor the bands characteristic of CsNO3.
Reaction of ( I ) with excess N204 at 2OoC proceeds quantitatively t o white, easily hydrolysable nitrosyl tetranitratoindate(II1) (3) :
N02[In(N03)4]
+ N204
+ NO[In(N03)41+ N20s
(3)
(1)
Instead of the band of the nitryl cation at 2360 cm-1, the
infrared spectrum of (3) contains a band due t o the nitrosyl
cation [3] at 2270 cm-1.
At 135°C in a high vacuum, compound ( I ) gives a clear,
volatile, colorless melt, with partial decomposition to white,
easily hydrolysable crystals of indium oxide nitrate (4) :
N02[In(N03)41
(1)
+ InON03
Photochemical Isomerization of the
Tricyclo[3,2,1,02,4]octeneSystem a Homovinylcyclopropane System
By Doz. Dr. H. Prinzbach, Dipl.-Chem. W. Eberbach, and
Dip1.-Chem. G.vonVeh
Chemisches Laboratorium
der Universitat Freiburg/Breisgau (Germany)
The exo-tricyclo[3,2,1,02~4]octene derivatives (fa), b. p.
136-14O0C/1O-3 mm, ( I b ) , m.p. 235 "C, ( i c ) , m.p. 80.5 'C,
and ( I d ) , m.p. 24O-24l0C, can be isomerized photochemically (Hanau Q-81 lamp fitted with a Uviol filter) to
the tetracyclo[3,3,0,02~~,0~~6]octane
compounds (2a)-(Zd)
[I]. Whereas the photoisomerization of the esters ( l a )
[Amax = 230.2 m p (E = 6770)] and (Ic) [Amax = 240.8 mg
(E = 517O)l [3] produces compounds (2a) and (2c) in yields
of 40 "/, at the most together with at least three other products, the valence isomerization of the acids (16) [Amax =
254.3 mp ( E = 6700)l and ( I d ) [Amax - 261.5 m p ( E = 5330)l
141 proceeds uniformly and in at least 90
yield [5].
+ 2 N204 + 0 2
(4)
Compound (3) decomposes at 90 "C t o white, readily hydrolysable indium nitrate (5) :
NO[ln(N03)4] + h(NO3)3
(3)
+ N204
(5)
The infrared spectra of compounds (1)-(3) and (5) contain
bands characteristic of covalent nitrates with -ON02
groupings [4].
By analogy t o the preparation of the new indium compounds,
the following thorium compounds were obtained:
436
white, readily hydrolysable
(6)
(9),
(8)
( I O j , white, readily hydrolysable
(a), R =
(c),
H, R' = C02CH3
R/R = CzH,,
R'= COzCK3
(b), R
H,
R'= COzH
fd), R / R = CzH4,
R'= C0$3
( 2 ) : m.p. 59°C; I R : n o C = C valence vibration bands;
UV in ethanol: only terminal absorption ( ~ 2 2 0= 440); N M R
in CC14: 6.25 T; 6.34 T [CH3O; (CH3O)zl; 7.27 T [I H, S];
7.5-8.5 T [6 H, MI; molecular weight: 280 (mass spectrum
[61).
( 2 6 ) : m.p. 228 "C.
( 2 c ) : m.p. 92.5OC; IR: no C-C valence vibration bands;
UV in ethanol: only terminal absorption (~220= 570); N M R
in CC14: 6.25 7 ; 6.31 T tCH3O; (CH30)2]; 7.05 T [I H, S];
7.98 T [4 H, AB spectrum; 6 * - 6 ~ = 46.5 cps; JAB = 9.0
cps]; 9.33 T [4 H, S]; molecular weight: 306 (mass spectrum
161).
( 2 d ) : m.p. 244-245 "C.
)
(2c) are very stable towards heat;
The tetracycles ( 2 ~ and
n o isomerization or fragmentation is observed up t o 250 "C.
The mass spectra [6] (CEC ZI- 103 C instrument; temperature
Aiigew. Cliem. internut. Edit.
1 Vol. 4(1965) 1 No. 5
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