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Dichlorotrinitrosylvanadium [V(NO)3Cl2]n.

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The two C- P distances iirc 1.76 A and arc thus significantly
shorter than those for C-P single bonds; the C-P-C angle
and 100' [2], and
is 105' (for comparison, (H3C),P: 1.87
(C6HS)3P: 1.83 A and 103" 131).
The planes of the two benzothiazole systems form a n ang:e of
only 3 O. The two sulfur atoms are 2.95 A apart and are thus
relatively close together.
New Heterocyclic Ring Systems
Containing Boron and Nitrogen
By Prof. Dr. F. Umland and Dipl.-Chcm. C. Schleyerbach
Anorganisch-Chemisches Institut der Universitat Miinster
(Germany) and
institut fur Anorganische Chemie der Technischen
Hochschule Hannover (Germany)
We have succeeded in preparing a series of five-membered
heterocyclic ring systems containing a boron atom together
with one to four nitrogen atoms in the ring:
1, I ,3,4-tetraphenyl-1-bora-2,5-dioxa-3-aza-4-cyclopentene
( I ) , m.p. 153 O C (prepared from N-benzoyl-N-phenylhydrsxylamine).
[I], m.p. 102 OC (prepared from N-nitroso-N-phenylhydroxylamine).
(3), m.p. 139 "C with decomposition (prepared from 1,3-diphenyl-3-hydroxytriazene [ 2 ] ) .
1 , I ,3,5-tetraphenyl- 1 - bora- 2,3,4,5 - tetraaza-4-cyclopentenc
(4), m.p. 130 "C with decomposition (prepared from 2,4-diphenyltetrazene [3]).
The figure shows the Y,Z-projection of a perchlorate anion
and of a phosphacyanine cation with averaged interatomic
distances in
and averaged bond angles. The distortions
out of the plane 2x + y + 22 = 2 are given in tenths of a n
Angstrom in the circles.
The phosphacyanine perchlorate ( I ) forms orange-red
needles which belong to the space group P i . Its lattice
constants are [4]:
- 11.673 * 0.009 B
8.412 i 0.006
11.713f 0.011
0: =
107'17'i 15'
66"41'& 15'
y = 95 "32' z t 15'
The density calculated for ( I ) from the volume of its unit
cell (1008 A,) and its molecular weight (456.9) is D, = 1.51
g/cm3; the value found by experiment was D, = 1.50 g/cm3.
A total of 3634 intensities were estimated visually from
Weissenberg photographs. The coordinates of the four
heavier atoms (2 S , P, and C1) were derived from a Patterson
synthesis. The positions of the remaining light atoms (18 C,
2 N, and 4 0) were then obtained from a Fourier synthesis
with the phases of the heavier atoms. After five cycles of
refinement, the R factor (i. e. the mean difference between
observed and calculated structural factors) was reduced to
16.4 "/,. From the error in the coordinates of about 0.01 A,
there results a mean error of about 0.02 A for the interatomic
distances and of 1-2" for the bond angles. Within the
limits of these errors both halves of the molecule have identical structures.
Received: December 1 Ith, 1964
[Z 8791700 IE]
German version: Angew. Chem. 77, 134 (1965)
[I] K . Dimroth and P. Hof mznn, Angew. Chem. 76, 433 (1964);
Angew. Chem. internat. Edit. 3, 384 (1964).
121 H . D . Springalland L. 0 . Brockway, J. Amer. chem. SOC.60,
996 (1938).
[3] J . J . Daly, J. chern. SOC.(London) 1964, 3199.
141 P . J . Wheatley, personal communication.
Angew. Chem. internat. Edit.
= N,
Z = 0
2= 0
X = 0,Y = N, Z
x = 0,Y =
(2), X
Vol. 4 (1965) / No.2
P-Aminoethyl diphenylborinate, Flavognost :O, and equimolar
amounts of the starting materials named above were dissolved
separately in the smallest possible volume of ethanol or a I : I
mixture of ethanol/benzene. The solutions \\ere combined
and a few drops of acetic acid were added to each mixture.
To obtain ( I ) and (2), the reaction mixtures here refluxed
for 30 min, but short boiling sufficed to form (3) and (4). T1.e
products crystallized out o n cooling and were recrystallized
from the same solvents, or ( 3 ) and ( 4 ) preferably from
methanol. If CupferronO (the ammonium salt of N-nitrosoN-phenylhydroxylamine) is used for preparing (2), a little
more than an equimolar amount of glacial acetic acid must
be added.
All four compounds are yellow and stable in air. Their stability in solution decreases in the series (1) >(2) > ( 3 ) >(4).
The diphenylboryl group can be replaced by a keavy metal
atom with aqueous solutions of heavy metal salts. However,
only those metal ions participate in this reaction which form
stable complexes with the chelate-forming compounds involved in (1)-(4). Hence the new compounds, especially ( I ) and
(2), are selective analytical reagents.
Received: December 14th. 1964; Supplemented: January 4th. 1965
887/710 IE]
German version: Angew. Chem. 77, 169 (1965)
[ I ] F. Uinlnnd and D.Thierig, Z . analyt. Chem. 197, 151 (1963).
[21 N . C. Sogani and S. C . Bhattachnrya, Analytic. Chem. 28, 81
[3] A . Wohl, Ber. dtsch. chem. Ges. 26, 1587 (1893).
Dichlorotrinitrosylvanadium w(NO)3C1&
By Priv.-Doz. Dr. W. Beck, Dr. K. Lottes, and
cand. chern. K. Schmidtner
Anorganisch-Chemisches Laboratorium
der Technischen Hochschule Miirlchen (Germany)
When nitric oxide is passed into a 0.2 M solution of VC14 in
anhydrous CC14, dehalogenation of the vanadium occurs and
dichlorotrinitrosylvanadium is obtained in almost quantitative yield.
VC14 + 5 NO -> V(N0)3Ci2 + 2 NOCI
The product is a light- to dark-brown solid depending on its
grain size; it is sensitive to moisture and is practically
insoluble in all the common organic solvents. In contrast to
the nitrosyl chlorides of iron [ l ] and cobalt [2], the new
compound cannot be sublimed and is therefore probably
polymeric in nature. Its infrared spectrum i n Nujol contains
N-0 absorptions at 1924 (s), 1761 (vs) cm-1 [3] plus two
bands at 309 and 261 cm-1 which can be assigned to V-CI
stretching vibrations. Comparison of the infrared spectrum
with those of other nitrosylmetal chlorides [3] showed that
[V(N0)3C12In has probably a polynuclear structure (1) with
terminal a n d bridging chloro ligands. This structure contains
sixfold coordinated vanadium with an inert-gas configuration
and has a trigonal bipyramidal arrangement of the N O
groups; these features are in agreement with the fact that
the compound is diamagnetic and gives only two N - 0
absorptions in the infrared.
Received: December 15th, 1964
[Z 880/701 IE]
German version: Angew. Chem. 77, 134 (1965)
precipitate. This melts at 70°C and is more stable than the
starting material. Here the Ga-H valence vibration Iies at
1986 cm-1, and the PMR signal for the trimethylamino group
is observed at 5.01 ppm (in benzene and relative to benzene
as standard). Here, too, no H --Ga signal could be detected.
Received: December 15th, 1964 IZ 882/703 IE]
German version: Angew. Chem. 77, 170 (1965)
111 Neither H3CGaC12 nor (H$&SiHCI could be detected by
spectroscopy in the products; these compounds might have
resulted from a reaction analogous to that of tetramethylsilane
with gallium trichloride [cf. H. Schmidbuur and W. Findeiss,
Angew. Chem. 76, 752 (1964); Angew. Chem. internat. Edit. 3,
696 (1964)l.
[ 2 ] GaH3 which is not stabilized by coordination decomposes far
below room temperature [3].
[3] E. Wiberg and M . Schmidt, 2. Naturforsch. 76, 577 (1952);
66, 172 (1951); N . N. Greenwood, Adv. inorg. Chern. Radiochem.
5,91 (1963). Cf. also D. F. Shriver, R. W. Parry, N . N . Greenwood,
A . Storr, and M . G. H . Wallbridge, Inorg. Chem. 2, 867, 1036,
1039, 1298 (1963).
Heterosiloxanes and t-Butoxy Compounds of
Aluminum, Gallium, and Indium
By Priv.-Doz. Dr. H. Schmidbaur
[I] W. Hieber and R. Nast, 2. anorg. allg. Chem. 244, 23 (1940).
[2] W. Hieber and R. Marin, Z . anorg. allg. Chem. 240, 241
(1939); W. Hieber and W. Beck, Z . Naturforsch. 13b, 194 (1958).
[3] W. Beck and K. Lottes, Angew. Chem. 76, 574 (1964).
Synthesis of Dichlorogallane HGaCl2
By Priv.-Doz. Dr. H. Schmidbaur, Dip1.-Chem. W. Findeiss,
and cand. chem. E. Gast
Institut fur Anorganische Chemie
der Universitat Marburg/Lahn (Germany)
Trimethylsilane reacts a t -20 O C with equimolar amounts of
gallium trichloride to form trimethylchlorosilane (99.5 ”/:
yield) and pure dichlorogallane.
+ GaC13
+ (H3C)3SiCI + HGaC12
When the chlorosilane is pumped off at -30 OC, a residue of
HGaC12 is obtained in 95 % yield as colorless crystals which
dissolve well and without decomposition a t low temperatures
in anhydrous solvents such as benzene, cyclohexane, or
diethyl ether [l].
Cryoscopic determinations of the molecular weight revealed
that HGaClz like GaCI3 is dimeric in benzene. It cannot
be kept unlimited at room temperature without decomposition, but rapid decomposition with evolution of hydrogen
begins only at its melting point of 29 “C [2]. Pyrolysis of the
compound at 150°C gives a quantitative yield of hydrogen
and gallium chlorogallanate (“gallium dichloride” GaC12).
(HGaC12)Z + Hz
+ Ga[GaC14]
The infrared spectrum of dichlorogallane has a somewhat
broadened but very intense band at 2018 cm-1 which is due
to the Ga-H valence vibration. This band is at much higher
frequencies than that for GaH3,N(CH3)3 [3] (1852 cm-1) and
indicates the higher force constant of the Ga-H bond in
dichlorogallane. The proton resonance spectrum of HGaC12
in benzene has no proton signal between -33 and + I 6 ppm
(relative to tetramethylsilane), but this is understandable In
view of the high spin and quadrupole moments of the gallium
When trimethylamine is passed into a solution of HGaClz in
benzene, colorless crystals of a n adduct HGaCI2.N(CH3)3
Institut fur Anorganische Chemie
der Universitat Marburg/Lahn (Germany)
We have succeeded in preparing organoheterosiloxanes with
Ga--0-Si and In-0-Si
structural units [1,2]. Trimethylgallium and trimethylindium etherates react fast even below
room temperature with equimolar amounts of trimethylsilanol to form the desired gallosiloxane and indosiloxane,
respectively, with liberation of methane.
+ Me3X. OEtz
CH3; Et
+ Et20
+ CH4 + Me3SiOXMez
(la). X
(Ib), X
A1 [3]
= In
The yields are almost quantitative. The products ( l u ) - ( f c)
occur only as dimers, having the four-membered ring
structure ( I ) , which probably has CZh symmetry judging
from infrared and N M R data [3]; compounds (Ib) and
( I c ) are surprisingly stable toward oxidation and hydrolysis.
H 3 C - \ C - d 0- ‘-CH3
(Zu), X = A1
(2b), X = G a
(2c), X = In
When anhydrous t-butanol is used instead of trimethylsilanol, the corresponding t-butoxydimethylmetal compounds
are formed. This type of reaction had already been described
for other alcohol components [4,5]. It is remarkable that
40.0 [b]
[a] Sublimes.
35/1 [a1
45/1.5 [a]
N M R 161
%ZH,Si, C
+ 17.0
+ 16.0
+ 8.7
[hl Waxy.
Angew. Chem. internor. Edit.
Vof. 4 (1965) / No. 2
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3cl2, dichlorotrinitrosylvanadium
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