www.elsevier.nl/locate/ica
Inorganica Chimica Acta 295 (1999) 248 – 251
Note
The nitrido complex (NEt
4
)[MoCl
3
(N)(OH)(MeCN)]
Christoph Janiak *, Savas ¸ Temizdemir
Institut fu ¨r Anorganische und Analytische Chemie, Uniersita ¨t Freiburg, Albertstr. 21, D-79104 Freiburg, Germany
Received 1 June 1999; accepted 14 July 1999
Abstract
The title compound tetraethylammonium-[(acetonitrile)trichlorohydroxonitridomolybdate(VI)] (1) is the product of the reaction
of the nitrido complex MoCl
3
(N) with (NEt
4
)Cl·H
2
O in acetonitrile. The acetonitrile and the nitrido ligand are arranged trans,
while the chloro and the hydroxo group form the equatorial plane of the pseudo-octahedral molybdenum coordination
polyhedron. Complex 1 may be regarded as a presumably first step in the hydrolysis of [MoCl
4
(N)]
-
and supplements earlier
results showing that [MoCl
4
(N)]
-
can be hydrolized to form [MoCl
4
(O)]
-
. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Molybdenum complexes; Nitrido complexes; Crystal structures; Hydrolysis
1. Introduction
Studies of the properties of high-valent metal – nitrido
complexes are receiving constant attention [1 – 7]. The
chloro(nitrido)molybdenum complexes X[Mo
VI
Cl
4
(N)]
(X =NMe
4
, AsPh
4
[8,9], PPh
4
[10]) and (NEt
4
)
2
-
[Mo
VI
Cl
5
(N)] and (NEt
4
)
2
[Mo
V
Cl
4
(N)] [11] are known.
The crystal structures of (AsPh
4
)[Mo
VI
Cl
4
(N)] and
(PPh
4
)[Mo
VI
Cl
4
(N)] have been elucidated [8,10]. In ad-
dition, the structure of (PPh
3
Me)
2
[Mo
V
Cl
4
(N)] is avail-
able, but the pyramidal [Mo
V
Cl
4
(N)]
2 -
-anion was
found disordered around a center of inversion [12].
2. Experimental
The infrared spectrum was measured on a Perkin–
Elmer 783 IR spectrometer. Magnetic measurements
were carried out on a Johnson Matthey magnetic sus-
ceptibility balance (MSB-Auto, Gouy balance) or on a
Varian O-300 NMR spectrometer according to the
method of Evans [13]. Acetonitrile was dried over
CaH
2
, refluxed and distilled under argon.
MoCl
5
(10 g, 36.6 mmol) was stirred for four days in
acetonitrile (MeCN, 60 ml). The solution slowly turned
brown with the formation of a brown precipitate of
MoCl
4
(MeCN)
2
[8,11]. The solvent was removed in
vacuo and the remaining solid stirred for 5 h with
toluene (60 ml). Then the toluene was decanted and the
settled solid dried in vacuo. From this MoCl
4
(MeCN)
2
(9.03 g, 28.2 mmol) and NaN
3
(1.84 g, 28.3 mmol) were
dissolved in MeCN (40 ml). Upon stirring of the mix-
ture a rapid gas evolution started which ended after 1 h.
A dark orange–red solution and a white precipitate
(NaCl) were obtained. The solution was decanted and
immediately treated with (NEt
4
)Cl···H
2
O (4.7 g, 28.3
mmol). The hygroscopic and partly wet (NEt
4
)Cl had
been dried at 100°C for 2 h. Soon the solution turned
red – brown and a white precipitate developed. After
stirring for 35 h, the solution was filtered and concen-
trated to about 20 ml. After 2 days at room tempera-
ture a yellow solid had precipitated and the solution
was filtered again. Cooling to -15°C yielded 5.9 g
(51%) of dark-red prismatic crystals. The crystals turn
opaque upon drying due to loss of the coordinated
MeCN solvent molecule. IR (KBr, cm
-1
): 3350 w br,
2990 m, 2040 s (CN), 1690 m, 1460 s, 1400 m, 1310 m,
1265 w, 1185 s, 1175 sh, 1055 m, 1035 m, 1005 m, 945
s, 915 s, 790 s, 705 s, 510 w, 380 m, 330 s. Anal. of the
* Corresponding author. Tel.: +49-761-203 6127; fax: +49-761-
203 6147.
E-mail address: janiak@uni-freiburg.de (C. Janiak)
0020-1693/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII:S0020-1693(99)00383-7