Synthesis and Structural Characterization of [Cu
20
Se
4
(µ
3
-SePh)
12
(PPh
3
)
6
] and
[Ag(SePh)]
ⴥ
Heather L. Cuthbert
a
, Andrew I. Wallbank
a
, Nicholas J. Taylor
b
, and John F. Corrigan
a,
*
a
London/Canada, Department of Chemistry, The University of Western Ontario
b
Waterloo/Canada, Department of Chemistry, University of Waterloo
Received June 3
rd
, 2002.
Dedicated to Professor Dieter Fenske (“Partner”) on the Occasion of his 60
th
Birthday
Abstract. Reaction of lithium phenylselenothiolate, generated in
situ from the reductive cleavage of PhSe-SiMe
3
with alkyl lithium
reagents and insertion of elemental sulfur, with triphenylphosphine
solubilized CuCl affords the molecular cluster complex [Cu
20
Se
4
-
(µ
3
-SePh)
12
(PPh
3
)
6
](1). The analogous reaction with AgCl yields
the extended structure [Ag(SePh)]
⬁
(2) in which an infinite layer of
Ag
I
atoms is capped on either side by µ
4
-SePh ligands.
Synthese und strukturelle Charakterisierung von [Cu
20
Se
4
(µ
3
-SePh)
12
(PPh
3
)
6
] und
[Ag(SePh)]
ⴥ
Inhaltsübersicht. Die Reaktion von Lithiumphenylselenothiolat, in
situ durch reduktive Spaltung von PhSe⫺SiMe
3
mit Lithiumalkyl-
Reagenzien und Insertion elementarem Schwefel gebildet, mit in
Triphenylphosphan gelöstem CuCl ergibt den molekularen Cluster-
komplex [Cu
20
Se
4
(µ
3
-SePh)
12
(PPh
3
)
6
](1). Die analoge Reaktion mit
AgCl ergibt [Ag(SePh)]
⬁
(2) mit einer unendlichen Schicht von
Introduction
The chemistry of late transition polynuclear metal-selenol-
ate (⫺SeR) complexes has received broad interest [1] and
has been augmented by the interesting photophysical
properties displayed by these clusters [2]. The synthesis of
higher nuclearity metal-selenolate cluster complexes has
been demonstrated using a variety of approaches including
cleavage of the Se⫺H bond via chalcogenolysis [3] (Eq. (1))
and direct insertion of a chalcogen element into metal
M⫺C bonds (Eq. (2)) [4]. The reaction of anionic selenolate
salts (Eq. (3)) also provides a route into M⫺SeR cluster
complexes [5]. Late transition metal(0) complexes have also
been shown to insert directly into diselenide bonds [6].
* Prof. Dr. John F. Corrigan
Department of Chemistry
The University of Western Ontario
London, Ontario
N6A 5B7 CANADA
Fax: (519) 661-3022
e-mail: corrigan@uwo.ca
Z. Anorg. Allg. Chem. 2002, 628, 2483⫺2488 WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044⫺2313/02/628/2483⫺2488 $ 20.00⫹.50/0 2483
1: space group P1
¯
, a ⫽ 17.9510(6), b ⫽ 18.1712(7), c ⫽ 31.4311(11)
A
˚
, α ⫽ 78.098(2), β ⫽ 82.905(2), γ ⫽ 70.012(2)°. 2: space group C2/c,
a ⫽ 5.8762(6), b ⫽ 7.2989(7), c ⫽ 29.124(2) A
˚
, β ⫽ 95.790(3)°.
Keywords: Copper; Silver; Selenium; Phenylselenolate; Cluster
compounds
Ag
I
-Atomen, die an jeder Seite durch µ
4
-SePh-Liganden abge-
deckt ist.
1: Raumgruppe P1
¯
, a ⫽ 17,9510(6), b ⫽ 18,1712(7), c ⫽
31,4311(11) A
˚
, α ⫽ 78,098(2), β ⫽ 82,905(2), γ ⫽ 70,012(2)°. 2:
Raumgruppe C2/c, a ⫽ 5,8762(6), b ⫽ 7,2989(7), c ⫽ 29,124(2) A
˚
,
β ⫽ 95,790(3)°.
L
n
M⫺X ⫹ HSeR 씮 L
n
M⫺SeR ⫹ HX (1)
L
n
M⫺R ⫹ Se 씮 L
n
M⫺SeR (2)
L
n
M-X ⫹ M’
⫹
[RSe]
⫺
씮 L
n
M-SeR ⫹ M’
⫹
X
⫺
(3)
L
n
M-X ⫹ Me
3
SiSeR 씮 L
n
M-SeR ⫹ XSiMe
3
(4)
Fenske and co-workers have demonstrated a wealth of
structural chemistry of copper and silver polynuclear selen-
ide and selenolate complexes when phosphine solublized
copper(I) salts are reacted with Se(SiMe
3
)
2
and/or
RSeSiMe
3
, these reactions driven by the formation of the
silane XSiMe
3
and metal-chalcogen bonding interactions
(Eq. (4)) [7]. The propensity of the heavier chalcogens to
adopt bridging versus terminal bonding modes favors the
formation of polynuclear, cluster complexes. Herein we
report on the synthesis of the polynuclear complex
[Cu
20
Se
4
(µ
3
-SePh)
12
(PPh
3
)
6
](1) and the sheet-like arrange-
ment of the homoleptic silver-selenolate [Ag(SePh)]
⬁
(2).
Results and Discussion
The selenium-silicon bond in PhSeSiMe
3
is cleaved with one
equivalent of butyllithium to generate the anion PhSe
⫺
in
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