Reactions of tin and lead with tricarbonylcyclopentadienylmolybdenum(II) and tricarbonylcyclopentadienyltungsten(II) chlorides

Article abstract of DOI:10.1023/A:1015341228059

Tin was oxidized with tricarbonylcyclopentadienylmolybdenum and tricarbonylcyclopentadienyl-tungsten chlorides to obtain polynuclear organometallic compounds [η⁵-C₅H₅M(CO) ₃]₂SnCl₂ (M = Mo,

Full text of DOI:10.1023/A:1015341228059

Russian Journal of General Chemistry, Vol. 72, No. 1, 2002, pp. 65 67. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 1, 2002,
pp. 72 74.
Original Russian Text Copyright
2002 by Piskunov, Maslennikov, Spirina, Maslennikov, Artemov.
Reactions of Tin and Lead
with Tricarbonylcyclopentadienylmolybdenum(II)
and Tricarbonylcyclopentadienyltungsten(II) Chlorides
A. V. Piskunov, S. V. Maslennikov, I. V. Spirina, V. P. Maslennikov, and A. N. Artemov
Research Institute of Chemistry, Lobachevskii Nizhny Novgorod State University, Nizhny Novgorod, Russia
Received July 4, 2000
Abstract Tin was oxidized with tricarbonylcyclopentadienylmolybdenum and tricarbonylcyclopentadienyl-
tungsten chlorides to obtain polynuclear organometallic compounds [ 5-C5H5M(CO)3]2SnCl2 (M = Mo, W).
The reactions of the above-mentioned oxidants with lead gave lead chloride and [ 5-C5H5M(CO)3]2 dimers.
Formal-kinetic regularities of tin oxidation with tricarbonylcyclopentadienylmolybdenum chloride in N,N-di-
methylformamide were found. Thermodynamic parameters of adsorption of the reagent on the metal surface
were determined.
Tricarbonylcyclopentadienylmolybdenum (I) and
tricarbonylcyclopentadienyltungsten (II) chlorides are
The highest yield of the target product is attainable
in a DMSO medium: 0.47 mol of a crude product
shown to be promising reagents in the synthesis of per 1 mol of the starting molybdenum or tungsten
polyorganometallic compounds by direct oxidation of
Group II metals [1 3].
organohalide. After double recrystallization from a
2:1 heptane benzene mixture we obtained com-
pounds III and IV as golden yellow crystals. Their
melting points, 200 and 225 C, respectively, were
consistent with those reported in [6]. The reaction in
DMF gave 0.41 mol of triorganometallic compound
per 1 mol of the starting oxidant. We emphasize that
this reaction favorably compares with the generally
accepted method of synthesis of compounds III and
IV, that involves the thermo- or photoinduced reac-
tion of [CpM(CO)3]2 dimers [M = Mo (V), W (VI)]
with tin(II) chloride, yielding CpM(CO)3SnCl3 deri-
vatives along with the target product [8, 9].
The aim of this work was to find out the possibility
and special features of the synthesis of polynuclear
organic compounds of nontransition Group IV metals
by their oxidation with compounds I and II in donor
solvents.
Metallic germanium fails to react with compounds
I and II for 500 h in any solvent, whereas tin reacts
with these compounds in tetrahydrofuran (THF), N,N-
dimethylformamide (DMF), dimethyl sulfoxide
(DMSO), and pyridine (Py) media even at room
temperature. Therewith, absorption bands typical of
the starting molybdenum and tungsten organohalides
Tetrahydrofuran and pyridine proved to be less
suitable for preparing compounds III and IV by reac-
tion (1). The yields of the target products in these
solvents are 0.28 and 0.12 mol per 1 mol of the start-
ing oxidant, respectively. The low yield in THF re-
sults from the low rate of the process, whereas in
pyridine a side reaction seems to occur.
{
CO 2055, 1983, and 1960 cm 1 (I) [4] and CO 2053,
1
1968, and 1947 cm (II) [5]} disappear from the IR
spectra of the reaction mixtures. Simultaneously, the
following absorption bands appear:
1958, 1940, and 1916 cm (reaction of tin with I)
2029, 2006,
CO
1
1
2023, 2002, 1948, 1931, and 1905 cm (reaction
CO
Lead, too, readily reacts with compounds I and II
in DMF and DMSO. However, these reactions occur
by a route different from reaction (1), giving dimers V
and VI and lead(II) chloride in quantitative yields.
Probably, the dilead derivative formed in the first
stage reacts with the starting oxidant.
of tin with II). According to [6, 7], these data point to
formation of [CpM(CO)3]2SnCl2 compounds [M =
Mo (III), W (IV)]. The metal weight loss corresponds
to the reaction of 0.5 mol of tin per 1 mol of the start-
ing oxidant. The above observables point to reac-
tion (1).
C5H5M(CO)3Cl + Pb
[C5H5M(CO)3]PbCl + C5H5M(CO)3Cl
[C5H5M(CO)3]2 + PbCl2.
[C5H5M(CO)3]PbCl, (2)
2C5H5M(CO)3Cl + Sn
[C5H5M(CO)3]2SnCl2, (1)
M = Mo, W.
(3)
1070-3632/02/7201-0065$27.00 2002 MAIK Nauka/Interperiodica

66
PISKUNOV et al.
Here k = kS20 and S0 is the number of active centers
[Cp(CO)3MoCl], M
0.1 0.2 0.3 0.4
per unit surface area.
0.0
0.5
Processing the experimental data in the coordi-
nates (COx/V)1/2 = f(COx) at CL = const and (CL/V)1/2
=
3
1
f(CL) at COx = const allowed us to calculate the ap-
parent rate constants of the reaction and the equilib-
rium constants of oxidant and ligand adsorption on
metal surface. From the temperature dependences of
these values we determined the apparent activation
energy and the enthalpy and entropy of reagent adsorp-
tion on the surface of zinc and cadmium.
1.5
2
2
1
0
1.0
0.5
1
ads
T, K
k, g cm 2 min
K
KLads
Ox
6
323
333
343
8.2 10
1.9 10
4.1 10
9.4
6.5
3.6
0.34
0.25
0.19
5
0
5
4
8
12
(74 2) J mol 1 K ,
C(DMFA), M
ads
ads
1
H
(30 1) kJ/mol;
S
Ox
Ox
HLads (26 1) kJ/mol; SLads (92 3) J mol 1 K ,
1
Rate of tin oxidation in the CpMo(CO) Cl DMF p-
3
xylene system on reagent concentrations at 323 K. C, M:
Ea 74 1 kJ/mol.
(1) CpMo(CO) Cl 0.2 and (2) DMF 8.6.
3
The value of the apparent activation energy points
to a reaction occurring in the kinetic mode [12].
Compounds V and VI were characterized by their
melting points and IR and UV spectra. The observed
parameters are consistent with those reported in [10].
The dependence of reaction rate on oxidant con-
centration does not obey a second-order kinetic equa-
tion, which may imply that the reaction occurs by
scheme (1). Probably, the initially formed tin(II)
derivative passess into bulk solution, where it reacts
with the starting oxidant.
The dependence of the rate of tin oxidation with
compound I in DMF on oxidant concentration fits
Langmuir’s isotherm, and the V = f(CDMF) plot passes
through a maximum (see figure). The shape of the
kinetic curves points to the fact that the oxidation
reaction is described by the Langmuir Hinshelwood
scheme with reagent adsorption on similar active
surface centers [11].
C5H5M(CO)3Cl + Sn
[C5H5M(CO)3]SnCl + C5H5M(CO)3Cl
[C5H5M(CO)3]2SnCl2.
[C5H5M(CO)3]SnCl, (8)
(9)
KOx
(4)
Ox + S0
OxS,
As shown in [2], the dependence of the rate of zinc
and cadmium oxidation on the donor number of the
solvent used [13] has an extremum. The rate maxi-
mum was observed in DMF. With tin, this maximum
falls on pyridine (COx 0.2 M, T 323 K).
KL
L + S0
LS.
(5)
(6)
k
OxS + LS
Products.
Here KOx and KL are the equilibrium constants of
oxidant and ligand adsorption, respectively, and k is
the rate constant of surface reaction.
Solvent Ethyl acetate THF DMF DMSO Py HMPA
DN(SbCl5),
71.8
83.7 111.3 125.9 139.6 162.5
kJ/mol
Similar mechanisms have been proposed for the
reactions of compound I in DMF with magnesium [1]
and zinc and cadmium [2].
V 104,
0.5
0.7 1.8 4.8 5.4 0.3
g cm 2 min
1
The rate of the process will be expressed by Eq. (7):
The extremal shape of the dependence of the rate
of tin solution is associated with selective ligand
adsorption on the metal surface. Some aspects of this
problem have been discussed in [14].
COxCLKOxKL
V = k
.
(7)
(1 + KOxCOx + KLCL)2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 1 2002

REACTIONS OF TIN AND LEAD
67
EXPERIMENTAL
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 1 2002