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The Preparation of Difluorodiazine and the Existence of Chlorofluorodiazine.

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Rhenium-Cobalt Enneacarbonyl
By Dr. Th. Kruck and Dipl.-Chem. M. Hofler
Anorganisch-Chemisches Laboratorium
der Technischen Hochschule Munchen (Germany)
Binuclear mixed metal carbonyk [L,(CO)j-nMM'(CO)m],
n=O, and their substitution products with o-phenanthroline
(L2 = C J ~ H ~ [I]
N can
~ ) be prepared by thermal decomposition of carbonyl salts such as [M(C0)6.nLn]+[M'(CO)mI(M = Mn(l), Re(1); M' = Co(-I), Mn(-I); m = 4 or 5). The
reaction is initiated by an intramolecular redox process. With
the loss of one molecule of CO per molecule of carbonyl salt
the two carbonyl radicals are linked by a metal-metal bond.
I n addition to the compounds MnCo(C0)s [2] and MnRe( C 0 ) ~ o[3], which were already known and were also prepared
by us [4] from t h e carbonyl salt [Mn(C0)6] [Co(CO),] or by
the reaction of [Mn(CO)&I.HCI with Na[Re(CO)21 and of
[Re(CO),j]CI.HCI with Na[Mn(CO)s], respectively, rheniumcobalt enneacarbonyl was now obtained:
[Re(C0)61 rCO(c0)d
60 " C
+ (CO)sReCo(CO)* f
(2), blue
to a radical content of at least 95 %; in the concentrated
solution this decreases rapidly and disappears within one
day. In 10-5 M solution in methylene chloride, (2) is considerably more stable and shows characteristic absorption
bands at 718 mi1 (log E = 4.85) and 995 m p (log E = 4.26).
The diamagnetic compound sublimes at 40-50 "C/lO-3 mni
yielding orange-brown, matted needles, m.p. 66 OC, decomposition point 148 "C. The infrared spectrum of the solution
in CC14 contains three intense, sharp bands at 2064, 2035,
and 1990 cm-1, i.c. in the range for terminaI CO groups; no
bands characteristic for bridging CO groups were observed.
Dry heating of [Re(C0)4(C12HsNz)] [Co(CO)4] produces the
deep-red o-phenanthrolinetricarbonylrhenium-tetracarbonylcobalt. According to the reaction
9 0 "C
~ R ~ ~ C ~ ) ~ ~ C I Z H S -N ~
(ClzHaNz)(CO)~ReCo(CO)~ CO
and to the infrared spectrum [vc-o = 2048(st), 2039(st-m),
2010(vst), 193 I(vst), and 1892(vst) cm-I] the bidentate ligand
is associated with the rhenium, and a pure rhenium-cobalt
bond exists. This structure is supported by a photoreaction
in tetrahydrofuran which yields the yellow compound
Received, August 6th, 1964
[ Z 806/629 IE]
German version: Angew. Chem. 76, 786 (1964)
[ I ] See also Th. Kruck and M . Hofler, Chem. Ber. 97,2289 (1964).
[2] K . K. Joshi and P . L . Pauson, Z. Naturforsch. 176, 565 (1962).
[3] A . N . Nesmeyanov, K. N . Anisimuv, N . E. Kolobova, and I . S .
Kolumnokov, Izvest. Akad. Nauk SSSR, Otdel. khim. Nauk 1963,
[4] Soon to be reported in detail.
Reduction of (2) by NaBH4 gave a hydrocarbon - so far
not completely pure - which might be formulated as ( 3 ) .
The action of one equivalent of (3) on ( I ) (10-5 mole/l)
in methylene chloride yields 1 . 6 10-5
mole/l of (2); coproportionation must therefore have occurred. The regeneration of ( I ) from (2) by perchloric acid in acetonitrile
must therefore be regarded as a disproportionation, during
which (3) is removed from the equilibrium by protonation.
Received, August 11th. 1964
[Z 8101634 IEI
German version: Angew. Chem. 76, 818 (1964)
.. .
[I] Cf. S . Hunig et al., Liebigs Ann. Chem., in the press: Tetrahedron Letters 1964, 181.
[la] We thank Prof. K . Hafner, Miinchen (Germany), for a
sample of azulene.
[ 2 ] D. H . Reid et al., J. chem. SOC.(London) 1963, 1422; IY61,
[3] Method: H . J . Friedrich, Z. Naturforsch. 196, 280 (1964);
Angew. Chem. 76, 496 (1964); Angew. Chem. internat. Edit. 3,
440 (1964).
A Stable Radical-Cation of a Hydrocarbon [l]
The Preparation of Difluorodiazine and the
Existence of Chlorofluorodiazine
By Prof. Dr. S. Hiinig, Dipl.-Chem. D. Scheutzow, and
Dr. H. J . Friedrich
By Dr. H. W. Roesky, Prof. Dr. 0. Glemser, and
cand. chem. D. Bormann
Chemisches Institut der Universitat Wiirzburg (Germany)
Guaiazulene [la], glyoxal, and perchloric acid in acetonitrile
readily yield the diperchlorate (1) [21; this is converted in
hot methanol into a blue monoperchlorate from which
perchloric acid in acetonitrile reforms the diperchlorate ( I ) .
Kirby and Reid [2] considered an acid-base reaction and
ascribed an allene structure (4) to the monoperchlorate.
We have found, however, that methanol acts as a reducing
agent. The blue monoperchlorate has structure (2) and
appears to be the first stable radical-ion of a hydrocarbon.
A 2.5 < 10-2 M solution of (2) in ethylene chloride/methylene
chloride ( I :9) shows, immediately on dissolution, a paramagnetic molecular susceptibility
: ;z
= 1232x 10-6
a paramagnetic moment 1
1 = 1.70 B. M. [3]. This corresponds
Anyew. Chem. internnt. Edit. [ Vol. 3 (1964)
I No. I0
Anorganisch-Chemisches Institut
der Universitat Gottingen (Germany)
The methods known for the preparation of difluorodiazine
[1--5] are either not very productive or very dangerous.
We have found a simple, safe method for continuous preparation of large quantities of N2F2 (1 -2 ml of trans-N;?Fz
per h). Technical sodium azide (98-99
pure) is allowed
to react at room temperature with elemental fluorine in a
revolving-cylinder reactor made of nickel. The N3F formed
as an intermediate is not isolated but is immediately decomposed by heating at 70-75 "C in a nickel spiral, so that
tpe reaction proceeds without explosion via the biradical
* N F to N2F2:
2 N3F
+ 2 N,+ 2.sF
70 1
During the thermal decomposition of N3F, excess fluorine
must not be present, otherwise the N2Fz is fluorinated to
NF3. This is prevented by having a large excess of sodium
azide in the reactor. Admixture of water vapor or preferably
of hydrogen fluoride t o the fluorine stream increases the
yield of N2F2. The product is contaminated with N20 [6]
and displays the characteristic infrared absorption band of
trans-N2Fz at 995 cm-1; after vacuum distillation the molecular weight was found to be 66.5 (calculated for NzF2: 66).
When the nickel spiral is heated to about 85 "C, cis-NzFz
[7] occurs together with frans-NzFn [8].
Sodium azide slightly dampened with water reacts with
chlorine in the rev0 :r g-cylinder reactor at room temperature to give chloroa de which is completely decomposed in
the nickel spiral by heating at 110 "C. When fluorine is mixed
with the chlorine stream ((212: F2 = 1 : 1) and the nickel spiral
is heated t o 120 "C, a gaseous product results which condenses in a trap cooled with liquid air to give a solid whose color
is yellower than that of chloroazide. Purification was not
possible since violent explosions occurred on condensation
and distillation in vucuo of this material. The infrared spectrum of the gaseous product showed the bands of cis- and
trans-NzFz and N z O , plus bands at 1540,1060, and 670 cm-1
and VN-CI frewhich were attributed t o VN-F,
The existence of the new compound chlorofluorodiazine
F-N=N-CI is therefore probable.
and N,N'-bis(dimethy1arsino)dimethylethylenediamine ( 4 )
[b.p. 94-96 OC/I nim], respectively, with very good yields
(80-90 %).
The A s - N bond in (2) is very easily broken using methyllithium [1,2]:
(2) + LiCH3 + (CH3)zAs-N-Li + As(CH3)s
The lithium (dimethy1arsino)methylamide ( 6 ) formed is very
reactive and is a useful starting material for further reactions;
for example, with trimethylchlorosilane it produces dimethylarsino(trimethylsily1)methylamine (7) [b.p. 66-68 "C/14 mm,
m. p. -50 "C.].
(6) + (CH3)3SiCl 4 (CH3)2As-&-Si(CH3)3 + LiCl
f 7)
Using (3) and phosphorus or arsenic trichlorides, one does
not obtain the halogen analogues of (4), but rather 2-chloro1,3-dimethyl-1,3,2-diazophospholidine
(8) [b.p. 98-100 "C/
14 mm, m.p. 1-3 "C] and 2-chloro-l,3-dimethyl-l,3,2-diazoarsenolidine (9) [b.p. 103-105 "C/14mm, m.p. 19-21 "C]
The yields are about 50 %.
Received, July 9th. 1964
[Z 778/618 IE]
German version: Angew. Chem. 76, 713 (1964)
[I] J. F. Haller, Ph.D.Thesis, Cornell University, Ithaca, N.Y.
(USA), 1942.
[2] US.-Pat. 3 109711 (June 15th, 1960); inventors: E. A.Lawton
and D . Pilipovich.
[3] C. B. Colburn, F. A. Johnson, A . Kennedy, K. McCallum, L. C.
Metrger, and C. 0 . Parker, J. Amer. chem. SOC.81, 6397 (1959).
[4] M . Schmeisser and P . Sartori, Angew. Chem. 71, 523 (1959).
[ 5 ] S. Morrow, P. D . Perry, and M . S. Cohen, J. Amer. chem.
SOC.81, 6338 (1959).
[6] If HF is mixed with the fluorine stream, the N20 content of
the product is low.
[7] R . L. Kuczkowski and E. B. Wilson, J. chem. Phyqics 39,
1030 (1963).
[8] c ~ s - N ~also
F ~ results on heating 1rans-NzF2. At 285 "C, for
example, there is an equilibrium between 13 "/b trans- and 87 9:
cis-N~F2.At 300 "C N2Fz decomposes into N2 and F2 [31.
The Synthesis of New Organoarsenic and
Organophosphorus Amines
By Dr. 0. J. Scherer and Prof. Dr. Max Schmidt
Received, August Ilth, 1964
[Z 809/633 IE]
German version: Angew. Chem. 76, 787 (1964)
[I] 0. J. Scherer and M . Schmidt, Angew. Chem. 76, 144 (1964);
Angew. Chem. internat. Edit. 3, 137 (1964).
[2] 0. J. Scherer, J. F. Schmidt, and M . Schmidt, Z . Naturforsch.
19b, 447 (1964).
Valence-Bond Isomerization of
By Dr. P. Heimbach
Max-Planck-Institut fur Kohlenforschung,
Miilheim/Ruhr (Germany)
Cis,trans-cyclodeca-1,5-diene(1) can be prepared in high
yield from butadiene and ethylene, using new nickel-based
x-complex catalysts [l]. The thermal rearrangement of ( I )
[I] (see Table 1) is stereospecific (>99.7 %). and yields cis1,2-divinylcyclohexane (2). The oxidative degradation of (2)
leads exclusively to cis-hexahydrophthalic acid (m. p. 190 to
191 "C) in 55 yield.
Institut fiir Anorganische Chemie
der Universitat Marburg/Lahn (Germany)
Table 1. Rearrangement of cis,trans-cyclodeca-l,5-diene(I)
1 I I I1
I I 1 1 I2i 1
60 "C [a]
Dimethylchloroarsine (1) reacts with methylamine or N,N'dimethylethylenediamine ( 3 ) in ether to form bis(dimethy1arsin0)methylamine (2) [b.p. 70-72 OC/14 mm, m.p.-34 "C],
2 (CH3)zAsCl + 3 CH3NH2
[a] Reaction temperature
( 1)
80 "C [a]
150 "C [a]
120 "C [a]
2 "C.
Acetylene, 2-butyne, and styrene also combine, like ethylene,
with butadiene on catalysts such as those used for the synthesis of cycloocta-1,5-diene [I] to give mono- or disub-
Angew. Chem. internat. Edit. 1 Voi. 3 (1964)
/ No. 10
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preparation, existencia, chlorofluorodiazine, difluorodiazine
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