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Heterosiloxanes and t-Butoxy Compounds of Aluminum Gallium and Indium.

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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.
(H3C)3SiH
+ 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
isotopes.
When trimethylamine is passed into a solution of HGaClz in
benzene, colorless crystals of a n adduct HGaCI2.N(CH3)3
152
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.
Me3SiOH
Me
=
+ Me3X. OEtz
CH3; Et
=
+ Et20
+ CH4 + Me3SiOXMez
(la). X
(Ib), X
(fc),X
CzHx
A1 [3]
Ga
= 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.
H3C FH3
H3C
X,
CH3
H 3 C - \ C - d 0- ‘-CH3
C?CH,
H3d
H3C CH3
A
‘
H3C 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
I
45.5
16.5
16.0
40.0 [b]
[a] Sublimes.
35/1 [a1
34-35/3
57-5813
45/1.5 [a]
N M R 161
%ZH,Si, C
-12.0
5.0
-
0.8
-82.0
I ‘CH3X
+49.0
+ 17.0
+
7.5
+46.0
+ 16.0
+ 8.7
[hl Waxy.
Angew. Chem. internor. Edit.
Vof. 4 (1965) / No. 2
despite their lower molecular weights, the carbon compounds
(2u)-(2c) are less volatile and higher melting than the
corresponding silicon analogues.
Received: December 15th, 1964 [Z 883/706 IEI
German version: Angew. Chem. 77, 169 (1965)
[ I ] Cf. H . Schmidbaur and W . Findeiss, Angew. Chem. 76, 753
(1964); Angew. Chem. internat. Edit. 3, 696 (1964); H. Schmidhaur, J . A. Perez-Garcia, and H. Hussek, unpublished results.
[2] The only gallosiloxane known heretofore was tris(trimethy1siloxy)galliurn: see H. Schmidbaur, Chem. Ber. 96, 2696 (1963).
[3] H. Schmidbnur, J. organometal. Chem. 1, 28 (1963); J. Amer.
chem. SOC.85, 2336 (1963); H . Schmidbaur and M . Schmidf, ibid.
arithmetic mean 5 of the two coupling constants is almost
exactly equal to the values found for the isosters: hexamethyldisiloxane: I 18.0; hexamethyldigermoxane: 125.5 cps
12.31.
II
1
I
84, 1069 (1962).
(41 E. G . Hoflmann and W.Tornau, Angew. Chem. 73,578 (1961).
[ 5 ] G. E. Coates and R . G. Hayrer, J. chem. SOC.(London) 1953,
25 19; G. E. Coates: Organometallic Compounds. Methuen, Lolldon 1960.
[6] Measured in CC14 as solvent on a Varian A 60 instrument with
60 Mc. 8 is in cps relative to tetramethylsilane as internal standard.
Trimethylaluminum Trimethylphosphorus Oxide
and Trimethylarsenic Trimethylgallium Oxide
By Dr. F. Schindler, Priv.-Doz. Dr. H. Schmidbaur, and
cand. chem. G. Jonas
Institut fur Anorganische Chemie
der Universitat Marburg/Lahn (Germany)
Trimethylphosphine oxide reacts rapidly in benzene with
trimethylaluminum etherate to form a 1 : 1 adduct with a
P-0-A1 bond.
The homologous ethyl compounds (2)-(4) are also formed
readily, and so is the analogous compound (5) with an
As-0-Ga
grouping obtained from trimethylarsenic oxide
and trimethylgallium etherate.
The chemical and spectroscopic properties of (1)-(5) indicate them to be isosteric with the hexaalkyldisiloxanes
RsSi-O-SiR3 (6) and hexaalkyldigermoxanesR3Ge-0-GeR3
(7). All the new compounds are surprisingly stable to heat
and exhibit no tendency to dissociate or to undergo intramolecular redox reactions up to about 150 'C. Cryoscopic
and osmometric determinations of their molecular weights in
benzene revealed that they are all monomeric. Because the
polarity of the P-0-A1 grouping is much stronger than that
of Si-0-Si or Ge-0-Ge bridges, the melting and boiling
points of the new oxides lie by more than 100°C above
those of the corresponding disiloxanes or digermoxanes.
The solubilities of (Z)-(4) in non-polar solvents other
than benzene are also lower than those of (6) or ( 7 ) . However
( 5 ) is much more soluble in such solvents than (1)-(4),
but cannot be distilled without decomposition.
The number, multiplicity, and area ratios of the proton
signals in the nuclear magnetic resonance spectra [ l ] of the
new compounds were invariably in accordance with the
theoretical expectations. The isosterism of the new oxides
with (6) and (7) is particularly obvious on comparison of
the coupling constants J(lH-13C). For ( I ) and for ( 5 ) , the
Angew. Chem. internat. Edit. 1 VOI.4 (1965)
1 NO. 2
108,s
I27
I27
-
-
109.0
134.5
n7.0-
I
1
Received. December 15th, 1964 [Z 8841707 (€1
German version: Angew. Chem. 77, 170 (1965)
[I] Measured in benzene as solvent on a Varian A 60 instrument,
60 Mc. The mean error for J(H-C) is about i- 1 cps.
[2] H . Schmidbaur, J. Amer. chem. SOC.85, 2336 (1963).
[3] H. Schmidbaur and I. Ruidisch, Inorg. Chem. 3, 599 (1964).
New Syntheses of the Adamantane Ring System
By Prof. Dr. H. Stetter, Dip1.-Chem. J. Gartner, and
Dr. P. Tacke
Institut fur Organische Chemie
der Technischen Hochschule Aachen (Germany)
3-Methylenebicyclo[3,3,l]nonan-7-one ( I ) [ l ] readily undergoes cyclization in the presence of acids to give I-hydroxyadamantane derivatives substituted at the 3-position.
(I/
(21,X = OH
(31, x = c1
(41, X = OC2H,
I jJ ,
X = NH-Ac
l6), X = NHZ
1,3-Dihydroxyadamantane (2) is obtained in almost quantitative yield from ( I ) with dilute sulfuric acid. Treatment
of ( I ) with hydrochloric acid produces 1 -chloro-3-hydroxyadamantane (3), m.p. 205.5 "C, while acids in ethanol lead
to 1 -ethoxy-3-hydroxyadamantane (4), m. p. 77.5 "C. Acetonitrile reacts with ( I ) under the conditions of a Ritter reaction
to give 1-acetamido-3-hydroxyadamantane(5), m. p. 220 OC.
The reaction of ( I ) with aqueous ammonia in a sealed tube
at 130 OC yields I-amino-3-hydroxyadamantane(6), m. p.
267 ' C .
The same principle can be applied to prepare polyethers (7)
of adamantdne by treating ( 1 ) with acids in inert solvents.
The same approach can be used to prepare adamantane
derivatives from 3,7-dimethylenebicyclo[3,3,l]nonane (a),
m.p. 75OC, which can be obtained from ( I ) in a Wittig
reaction; ring closure of (8) with acids gives l-methyladamantanes containing substituents at the 3-position.
Thus, I-hydroxy-3-methyladamantane(9), m.p. 131 'C, and
l-methyl-3-methoxyadamantane(l0), b.p. 99- 100 "Cjl3 mm,
153
117.8
-.
.
125.8
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