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Barium Halogenonitrides.

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fairly large excess of trimethylchlorosilane with 1 mole of
acetamide under the same conditions produced in good yield
u carboxamide which is bis-silylated at the amide group, viz.
the hitherto unknown bis(trimethylsilyl)acetamide (I).
This is a colorless liquid (b.p. 67.SoC/30 mm) and is very
sensitive towards hydrolysis. It proved possible in the same
way t o transform acrylamide into bis(trimethylsilyl)acrylamide (2), a colorless liquid of b.p. 73.SoC/22 mm. Investigations are in progress to decide between the two
structures possible in each caw.
dSi-,andlor R . C-N-
” .
Miss A. Sieburg carried out the invcstigations on the rhenium
Refcived, December Sth, 1962 [Z 404/228 1E)
[*I At present situated in the Max-I’lanck-Institui fur Chemie
(Otto-Hahn-lnstitut)in Mainz, Gerniany.
[I] E. Weise. 2. anorg. allg. Chem. 283,377 (1956).
121 J. L. Hoardand W . B. Vincent. 3. Amer. chem. SOC.61,2849
( 1939).
[3] R. D. Peacock, Chem. and Ind. IVSS, 1453.
(41 H.Bode and W.Wen& 2.anorg. iillg. Chem. 26Y. 165 (1952).
[5] Density determination: cf. K. Srhworhau, Z. Naturforsch. 170
630 (1 962).
(1) R
Complexes of MoIybdenum(II1) with 1,3-Diketones
(2) R == H2C ICH
By DipLChem. K. Christ and Prof. Dr.
Limburg and Post [31 thought that they had prepared (I) by a
reaction between ketene and hexamethyldisilazdne,
[(H3C)3Si-NH-Si(CH3)3]. The very high boiling point
(61.5°C/0.15 rnm) differs from that of our product, and the
analytical data do not correspond to the required values; this
proves that these authors had not obtained the substance
Received, December 4th. 1962
[Z4051229 I€]
lnstitul fur Physikalische Chemie
der Universitiit FrankfurtlMain (Germany) [*I
We have prepared the following co-ordination compounds
of trivalent molybdenum:
b -c‘
“!!I I
[ I ] 17th Communication on organosilicon compounds; 16th
Communication: L. Birkofer, A. Rirrer. and H. Dickopp, Chem.
Ber., in the press.
12) L. Birkofer, A. Ritter. and H. Dickopp, Chem. Ber., in the
131 W. W.Limburg and H.W. Post, Rec. Trav. chim. Pays-Bas
81, 430 (1962).
Preparation, Properties and Crystal Structure of
Potassium Hexafluorotechnetate(1V)
By Dr. K. Schwochdu and Prof. Dr. W.Herr
Arbeitsgruppe Jnstitut fur Radiochemie” der
Kernforschungsanlage Jiilich (Germany) and lnstitut fiir
Kernchemie der Universitiit K6ln (Germany) [*]
In analogy with the preparation of the corresponding
rhenium compound [I], we obtained K I (99TCF6) on melting
KzvcBr6) with K HF2. Potassium fluorotechnetate was
isolated in a pure state and in 60-70 % yield by recrystallization from water as pale pink, hexagonal platelets. The
solubility of the salt at 25 O C was 1.5 g in 100 g of water.
The absorption spectra of the (T‘CF6)2- and (ReF6)2- ions
are extensively similar in the visible, ultraviolet, and infrared
regions, as was to be expected. While the other hexahaIogen
complexes of tetravalent technetium and rhenium do not
absorb in the infrared spectral region of 4OOO-400 cm-1, an
intensive band was found for K2(TcF6) at 574 cm-1 (17.4
(z), and one for Kz(ReF6) at 550 cm-1 (18.2 (z); these are to
be assigned to the Tc-F and Re-F oscillations respectively.
The resistance of the fluorotechnetate to hydrolytic decomposition is particularly noteworthy. Chloro-, bromo-,
and iodotechnetate (IV) all undergo hydrolysis even in
weakly acid solution but (TcF~)~only in hot conc. aqueous
According to X-ray structura1 investigations, K2ncF6)
crystallizes a t room temperature in the trigonal Kz(GeF6)
type [2] with lattice constants a = 5.807 j, 0.002 A and
c = 4.645 f 0.002 A, and is isomorphous with Kz(ReF6) [1,3]
and a modification of Kz(MnF6) [4] at low temperature.
The density of potassium fluorotechnetate was measured as
p = 3.58 f 0.01 dcm3 [4]. It follows from this and from the
crystal structure that the unit cell contains one formula
Angew. Chem. internut. Edit.
VoI. 2 (1963) I No. 2
H.L. Schliifer
The following diketones were uscd: (I) acetylacetone [I],
(2) trifliioroacetylacetone,(3) bcnzoylacetone, (4) dibenzoylmethane, and (5) thenoyltrifluoroacetone.
The ketones (I) and ( 2 ) were treated with K3[MoIuClb] in
aqueous methanol at room tempcrature, the acid formed
being buffered with ammonium acetate. The compounds
precipitate after fairly prolonged standing. Molybdenum(lll)tris-acetylacetonate was recrystallized from a mixture of nhexane and tetrahydrofuran (2:l), while n-hexane was used
for molybdenum(l1l)-tris-trifluoroacctylacetonate.
Solubility difficulties arise with ketones (3), (4), and (5) but
can be circumvented by using a tcrnary mixture of dioxanl
methanol/water as rextion medium and ( N H & [ M o ” ~ ~ s (HzO)] as starting material. The required compounds were
then obtained by fairly prolonged and vigorous stirring at
room temperature followed by evaporation of the solvent in
vacuo. The products are deep rcd-brown to black. They
dissolve in organic solvents such as benzene, tetrahydrofuran,
CC14, and partially in n-hexane to give deep red-black
solutions. Scveral of the compounds become hot spontaneously in air. As the size of the organic ligand increases, the
tendency to give tarry products during this process grows.
All manipulations must be carried out under highly purified
nitrogen, and it is essential to remove carefully any traces
of dissolved oxygen from the solvents.
The preparation of the compounds mentioned and the
results of investigations of their optical and magnetic properties will be published in the near future.
Received, Decemher 7th. 1962 [Z4101236 IEl
[I] Molybdenum(llI)-trisacetylacetonate has also been prepared
by M . L. Larson and F. W. Moore, J. inorg. Chem. 1.856 (1962).
Barium Halogenonitrides
By Prof. Dr. P. Ehrlich, Dr. E. Koch
and DipLChem. V. Ullrich
Jnstitut f i r Anorganischc und Analytische Chemie
der Univcrsit‘it GieBen (Germany)
Continuing an earlier investigation [I] of the chloronitrides
of alkaline earth metals, in which the existence of the compounds CazNCl and BazNCl was verified, the systems
Ba3Nz/BaBrz and Ba,N2/BaIz were examined. On fusing
BaBr2 and Ba metal in a molar ratio of 1 :3 in the presence of
nitrogen, a black lustrous product was obtained, which was
identified as a hitherto unknown compound, Ba2NBr. It is
distinguished by a melting point maximum at 920"C in the
phase diagram of the system Ba3NzlBaBr2. The two eutectics
are at 19 mole- % Ba3N2 and 610 "C and at 87 mole- % Ba3N2
and 828 "C.
In the phase diagram of the Ba3NdBalz system, there is only
one melting point maximum, viz. at 10 mole-% Ba3N2 and
81OoC,with accompanying eutectics at 2 mole- "/, Ba3N2 and
692"C and at 20 mole- % Ba3N2 and 660"C. A product with
10 mole-% Ba3N2 crystallizes as pale yellow, matted, fine
needles and displays characteristic X-ray interference patterns which indicate a compound of formula Ba6N19. The
compounds Ba2NBr and BagNl9 disintegrate readily on exposure to the atmosphere.
Received, December 7th. 1962
[Z 4071238 IEl
[I] P. €hrlich and W.Drissmann. Angew. Chem. 70, 656 (1958).
Synthesis of Aromatic or Heterocyclic
Substituted Alkenes from Ketones
Shell Grundlagenforschung-GmbH.,
SchloD Birlinghoven (Germany)
The base-catalysed addition of dialkyl phosphites onto ketones generally yields dialkyl u-hydroxyphosphonates (I) [I].
In certain cases, however (X= CCI3, P(O}(OR2, CN, or
CO-CH3) [2], phosphates (2), produced by a rearrangement, or their secondary products, (X = CCI,), viz. enolphosphates, were isolated.
t HP-OR'
Hd b R '
By Dr. 0.Scherer and Prof. Dr. Max Schmidt
lnstitut f i r Anorganische Chemie
cler Univarsitiit MarburdLahn (Germany)
Sodium bis(trimethylsilyl)imide [(CH3)3Si]2NNa (I) [l] is
not only suitable for stepwisc nucleophilic degradation of
elemental sii1fur (s8 ring) [2] but is also able to effect easy
splitting of S-S bonds in stilfunc derivatives, as we have done
using alkyl- and aryl-disulfans. According to the equation:
+ R.4-S.
.R -+ R- S . .N[Si(CH3),Jz
+ R -S-Na
the following unsymmetrical rnonosulfanes were formed
almost quantitatively in bcnzene solution:
Phenyl-bis(trimethylsilyl~~ininosulfane(2), b.p.87-8S°C/1 nun,
n-Butyl-bis(trimethyIsilyl);iininosulfane, b.p. 71-72"C/l mm,
Ethyl-bis(trimethylsilyl)aminosulFane, b.p. 36-37"C/l mm.
The reactivity decreases in the order C6H5 > C2Hs > C4H9.
We also obtained (2) by the reaction
By Dr. U. Hasserodt and Prof. Dr. F. Korte
Alkyl- and Aryl-aminosulfanes Containing
N-Silyl Groups
+ Cl
S -GHs + GHs-S-N
However, because of the disilgreeableproperties and generally
very complicated preparation of chloro-organosulfanes
("sulphenyl chlorides"), riucleophilic scission of disulfanes
according to equation (a) is a much better synthetic route
leading to orguno-aminosulfanes. A corresponding scission
of long-chain organic sulfanes is currently under examination.
Received, December 12th. 1962
[Z 4091237 1EI
[I] U.Wannagaf and H.Nieclerprucm, Chem.Ber.94,1540 (1961).
12) 0.Scherer and M. Schmiilt. Natutwissenschaften,in the press.
Acetylene Derivatives from a Fragmentation
We have now found that the u-hydroxyphosphonate + phosphate rearrangement also takes place in presence of catalytic
quantities of base when X is an aromatic group. However,
the phosphates are difficult to isolate when R contains C-H
bonds in the u-position to the C-0 group; they are then
extremely unstable and decompose slowly at room temperature or rapidly on distillation under reduced pressure, in
both cases liberating considerable quantities of dialkyl phosphate and the corresponding olefin. The olefins may be
isolated by the following procedure:
Equimolar quantities of p-chloroacctophenone and diethyl phosphite
are treated with 3-10 mole-% of NaNH2. keeping the temperature
below 50°C. The contents of the flask solidify. forming the a-hydroxyphosphonate (1). m.p. I13 "C, and are then maintained at 140°C for
90 minutcs. During this time, the pH falls to about 3. After dissolving
in water. several extractions with cyclohexane are performed. and pure
pchlorostyrene as verified by sas chromatography is obtained in 60 "/.
yield by distillation of the organic phase.
By Prof. Dr. K. Bodendorf and Dr. P. Kloss
der Technischcn Hochschule Karlsruhe (Germany)
The reaction of ketones with the Vilsmeyer-complex (I) gives
u,&unsaturated chloroaldchydcs [I 1.
By treating acetoveratrone (2) with (I), we were able to
obtain ~chloro-3,4-dimelhoxycinnamaldehyde (4) (m.p.
116-1 17 "C) in 60% yield, by hydrolysis of the intermediate
In the same manner,styrene was prepared from acetophenone
(71 %), pbromostyrene from p-bromoacetophenone (60%),
2-vinylthiophene from 2-acetylthiophene (56"/,), and stilbene
from benzyl phenyl ketone (8 I x).
Received, December 11th. 1962 IZ4081241 1El
.. .
[I] Y.S. Abramov, Zhur. Obshchei Khim. 22,647 (1952). Chem.
Abstr. 47, 5351 (1953).
[2] W. Lorcnz, A. Henglein, and G. Schrader, J. Amer. chern.
SOC. 77,2554(1955);S.J. Ntch and K. Muedritzer, ibid. 84, I876
(1962); L. A. R. Hall, C. E. Sfcphens and J . 1. Drysdale, ibid. 79,
1768 (1957); V. A. Kuklitin, V.S. Abramov and K. M. Orekhovn,
Proc. Acid. Sci. USSR. 128,903 (1959).
With alkali, (4) gives 3,4-dimethoxyphenylacetylene(5)
(m.p. 72-73 "C)[2]in approximately SO% yield.
In this reaction, the unstable intermediate (6) obviously
arises by addition of a hydroxyl ion onto the aldehyde and
Angew. Chrnr. iirlcwr(rt. Edit.
Yol. 2 (1963)
I No. 2
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halogenonitrides, barium
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