The Solubility of Bis(cyclopentadienyl)samarium(II) and Implications
for the Reaction of Samarium Metal with Bis(cyclopentadienyl)mercury(II)
Glen B. Deacon*
Clayton, Victoria/Australia, Monash University, Chemistry Department
Dirk Stellfeldt, Gerd Meyer
Koln, Institut fur Anorganische Chemie der Universitat
Received Dezember 3rd, 1999.
Abstract. Bis(cyclopentadienyl)samarium(II) has been shown
to be insoluble in thf : ether mixtures, hence it cannot be iso-
lated as a soluble product from the reaction of samarium
with HgCp2 in thf : ether.
Beletskaya et al. have reported the isolation of [SmCp2(thf)2]
from the filtrate after the redox transmetallation reaction of
samarium metal with HgCp2 in tetrahydrofuran (thf) [1] and
tetrahydrofuran : diethyl ether (5 : 1, v/v) [2].
Sm + HgCp2 SmCp2 + Hg (1)
We reinvestigated this reaction [3], as well as the related re-
dox transmetallation between Sm metal and TlCp in
thf : ether (5 : 1, v/v) [4], the conditions of the full paper [2],
because it has been reported that [SmCp2(thf)] [5] and
[SmCp2(thf)2] [6] are insoluble in thf, and there is little rea-
son to believe that addition of diethyl ether should enhance
the solubility. From both reactions, SmCp3 was isolated in
high to near quantitative yield.
2 Sm + 3 HgCp2 2 SmCp3 + 3 Hg (2)
Sm + 3 TlCp SmCp3 + 3 Tl (3)
Subsequently, the original authors reported formation of a
soluble samarium(II) species claimed to be SmCp2, by reac-
tion (1), this time in a changed solvent system thf : ether
(1 : 1.5, v/v) [7]. Since they accepted that SmCp2 is insoluble
in thf alone [7], the key issue now is whether it is soluble in
thf : ether. Since we recently prepared SmCp2 for study of its
oxidation reactions [8], we were in position to resolve this is-
sue, and we report that solids with the composition
[SmCp2(thf)], [SmCp2(thf)1.5] and [SmCp2(thf)2] are all inso-
luble in thf : ether, hence [SmCp2(thf)2] (or lower solvates)
can not be isolated from the Sm/HgCp2 reaction as a soluble
species.
Bis(cyclopentadienyl)samarium(II) was prepared by the
metathesis method in thf [6], and because of the variation in
the thf content reported [2, 5, 6], we investigated the effect
* Prof. Dr. G. B. Deacon,
Chemistry Department,
Monash University,
Clayton, Victoria 3168,
Australia,
Fax: (61)3 99 05 45 97
E-mail: Glen.Deacon@sci.monash.edu.au
Z. Anorg. Allg. Chem. 2000, 626, 623624 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
Keywords: Samarium; Bis(cyclopentadienyl)samarium(II)
of drying on the thf content. Thus, drying for 0.5 h at room
temperature provided the solid [SmCp2(thf)2]. After 3 h
drying, the composition was [SmCp2(thf)1.5], and after 15 h
drying, [SmCp2(thf)]. We have been unable to obtain single
crystals of solvated SmCp2. Solubilities of all materials
(though lower solvates presumably revert to [SmCp2(thf)2]
on treatment with thf) were tested in thf : Et2O, mainly
1 : 1.5, but in one case 1 : 2 to give ether a better chance to
influence the solubility. The compound was stirred with the
solvent for a prolonged period under purified argon. Filtra-
tion in each case gave an insoluble purple precipitate and
a colourless filtrate. Evaporation in representative cases
yielded no purple solid.
Although it is unnecessary for us to explain the results of
Beletskaya et al. [1, 2, 7], we make the following observa-
tions. We accept that use of sufficiently reactive Sm metal
could lead to formation of some SmCp2, but this should be
filtered off with excess Sm metal and mercury. We have seen
some insoluble purple material in TlCp/Sm reaction mix-
tures [9], though we normally obtain high yields of SmCp3
from the reaction [4]. Beletskaya et al. report low solubility
side products in their reaction mixtures but these were con-
sidered to be bimetallics [2]. It is also possible to obtain
SmCp2 in a finely divided state that passes through a normal
porosity frit. We have observed that SmCp2 formed by the
exchange reaction between bis(2-phenylindol-1-yl)sama-
rium(II) [10] and cyclopentadiene (eq. 4) in thf partly passes
through a frit, but on standing, settled as a fine purple preci-
pitate in a colourless supernatant liquid [11], consistent with
insolubility.
Sm(pin)2 + 2 CpH SmCp2 + 2 pinH (4)
Some of our product from the metathesis preparation [6]
passed through a porosity 4 frit, but settled out on standing
leaving a colourless supernatant liquid.
If HgCl2-activated Sm [1, 2, 7] retained some SmCl2 or
HgCl2, then a soluble SmIICpCl species might be obtained,
which would undergo the reported reduction reaction of the
solutions prepared by Beletskaya et al. [7].
00442313/00/626623624 $ 17.50+.50/0 623

Experimental Part
All manipulations were carried out under purified argon
using Schlenk techniques and dry boxes (M. Braun, Gar-
ching). Tetrahydrofuran and diethylether were dried over
potassium/benzophenone and sodium-potassium-alloy/ben-
zophenone respectively. Bis(cyclopentadienyl)samarium(II)
was prepared by the metathesis reaction [6]. After drying for
0.5 h under vacuum at room temperature, the product was
[SmCp2(thf)2] (424.76): Sm 35.92 (calc. 35.40%); after drying
for 3 h, the product had the composition [SmCp2(thf)1.5]
(388.71): Sm 39.34 (calc. 38.68%); after drying for 15 h, the
product was [SmCp2(thf)] (352.66): Sm 42.30 (calc. 42.64%).
Solubility studies
In each case, [SmCp2(thf)n] (n = 1, 1.5 or 2) was suspended
in thf : ether. After stirring overnight (> 12 h) at room tem-
perature, the resulting suspension was filtered through a por-
osity 4 (fine porosity) frit, collecting a purple solid on the
frit, and giving a colourless filtrate. Evaporation of represen-
tative filtrates provided no trace of a purple solid.
Systems examined:
[SmCp2(thf)2] (0.130 g) in thf (10 ml)/Et2O (15 ml)
[SmCp2(thf)2] (0.097 g) in thf (6 ml)/Et2O (9 ml)
[SmCp2(thf)1.5] (0.155 g) in thf (10 ml)/Et2O (20 ml)
[SmCp2(thf)] (0.031 g) in thf (6 ml)/Et2O (9 ml)
624
G. B. Deacon, D. Stellfeldt, G. Meyer
This work was supported by the Fonds der Chemischen In-
dustrie, Frankfurt am Main, and the Australian Research
Council. D. St. is especially grateful for a Kekule stipend.
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Z. Anorg. Allg. Chem. 2000, 626, 623624