SYNTHESIS OF BIS(TRICARBONYLCYCLOPENTADIENYLMOLYBDENUM)BISMUTH(III)
1055
lated the compound [CpMo(CO) ] Bi (IV), which was bound to magnesium or indium. Thus, reaction of II
3
3
characterized by IR spectroscopy (
2005, 1965,
2004, 1966,
with bismuth in a mixed solvent follows scheme (7):
CO
1
1
1
930, 1895 cm ; published data [7]:
929, 1896 cm ) and elemental analysis (found, %:
CO
1
n[CpMo(CO) ] BiCl + 3M
3 2
Bi 22.6; Mo 30.1. C H BiMo O . Calculated, %:
2
4
15
3
9
2[CpMo(CO) ] M + nBi + MCl ,
(7)
3
n
n
Bi 22.1; Mo 30.5). Compound II and magnesium
react in a 2 : 1 ratio; with indium, this ratio is 3 : 1.
Thus, the reaction equation is as follows:
M = Mg, n = 2; M = In, n = 3.
Such a reaction pattern can be explained as fol-
lows. At a low DMSO content, the reaction follows
two parallel pathways: that described by Eq. (3) and
metal interchange of polynuclear bismuth derivatives
with magnesium or indium. At a high DMSO content,
the rate of the metal interchange exceeds that of for-
mation of IV.
n[CpMo(CO) ] BiCl + M
3
2
2
/3n[CpMo(CO) ] Bi + (n 2/3n)Bi + MCln, (3)
3 3
M = Mg, n = 2; M = In, n = 3.
Let us consider the scheme of reaction (3) in detail.
According to [3, 10], organometallic halides react
with magnesium to give analogs of Grignard reagents:
EXPERIMENTAL
RmCl + Mg
RmMgCl,
(4)
The IR spectra were taken on an IKS-29 spectro-
photometer.
where Rm is an organometallic fragment.
All manipulations with organometallic compounds
were performed in an inert atmosphere.
m
According to [10], R MgCl can react with a sec-
m
ond R Cl molecule to give a symmetrical derivative:
In the study, we used Bi of pure grade, TU (Techni-
cal Specifications) 3153-54; Mg of MCh-1 grade,
GOST (State Standard) 804 56; and In of IN-8
grade, GOST 10297 75. Compound I was prepared
as described in [13]; it contained no less than 99%
main substance, according to analysis for chlorine [9]
and molybdenum [14]. Organic solvents (chemically
pure grade) were dried by common procedures [15].
m
m
m
R Cl + R MgCl
R
+ MgCl2.
(5)
2
Reduction of II with sodium naphthalenide also
yields compound IV and bismuth. Apparently, unsta-
ble polynuclear dibismuthine arising in the first step
disproportionates by scheme (6) suggested previously
for tetraphenyldibismuthine [11]:
Polynuclear organometallic compounds were min-
eralized according to [16]. Analysis for chlorine,
magnesium, indium, bismuth [9], and molybdenum
3
{[CpMo(CO) ] Bi}
4[CpMo(CO) ] Bi + 2Bi. (6)
3 3
3
2
2
When the reactions of II with magnesium and indi-
[14] was performed by common procedures.
um are performed in a mixed solvent (THF DMSO),
a new pathway arises. At a low DMSO content (THF :
DMSO = 5 : 1), the color of the reaction mixture
changes from green to red and then gradually disap-
pears. At a higher DMSO content (THF : DMSO =
REFERENCES
1
. Ioffe, S.T. and Nesmeyanov, A.N., Metody elemento-
organicheskoi khimii. Magnii. Berillii. Kal’tsii.
Strontsii. Barii (Methods of Organometallic Chem-
istry. Magnesium. Beryllium. Calcium. Strontium.
Barium), Moscow: Akad. Nauk SSSR, 1963.
1
: 1), the red coloration does not appear at all, and
the initial green solution decolorizes.
The ratio of the reacted metal and oxidant is in this
case 3 : 2 for magnesium and 1 : 1 for indium. The
reaction products contain bismuth in the amount of
2
3
. Sheverdina, N.I. and Kocheshkov, K.A., Metody
elementoorganicheskoi khimii. Tsink. Kadmii (Methods
of Organometallic Chemistry. Zinc. Cadmium),
Moscow: Nauka, 1964.
1
mol per mole of II. Treatment of the liquid phase
with HgCl2 yields CpMo(CO) HgCl. The organo-
3
molybdenummercury derivative was isolated in the
amount of 2 mol per mole of reacted II and identified
by comparing its melting point and IR spectrum with
. Piskunov, A.V., Spirina, I.V., Artemov, A.N., and
Maslennikov, S.V., Zh. Obshch. Khim., 2000, vol. 70,
no. 9, p. 1409.
the published data (mp 190 C dec.;
2024, 1954,
CO
1
936 cm 1 [12]). Formation of CpMo(CO) HgCl
4. Piskunov, A.V., Maslennikov, S.V., Spirina, I.V.,
Maslennikov, V.P., and Artemov, A.N., Zh. Obshch.
Khim., 2001, vol. 71, no. 5, p. 714.
3
proves, by analogy with [3, 6], the presence in the re-
action mixture of compounds containing CpMo(CO)3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 7 2003