Journal of Organometallic Chemistry 579 (1999) 321 – 327
Synthesis and characterization of new allyl palladium complexes with
thionate ligands; X-ray molecular structures of
[Pd
3
(
3
-C
4
H
7
)
3
{pm(Me)
2
S}
2
](CF
3
SO
3
) and [Pd{pm(Me)
2
S}
2
],
3
-C
4
H
7
=
3
-2-MeC
3
H
4
, pm(Me)
2
S = Pyridine-4,6-dimethyl-2-thionate
Rafael Ferna ´ndez-Gala ´n
a
, Blanca R. Manzano
a
, Antonio Otero
a,
*, Nicolas Poujaud
b
,
Marek Kubicki
b
a
Departamento de Quı ´mica Inorga ´nica, Orga ´nica y Bioquı ´mica, Uniersidad de Castilla -La Mancha, Facultad de Quı ´micas,
E-13071 Ciudad Real, Spain
b
Laboratoire de Synthe `se et d’Electrosynthe `se Organome ´talliques (UMR 5632), Uniersite ´ de Bourgogne, Faculte ´ des Sciences Gabriel,
6 Bd. Gabriel, E-21000 Dijon, France
Received 23 November 1998
Abstract
The reaction of [Pd(
3
-C
4
H
7
)]CF
3
SO
3
(
3
-C
4
H
7
=
3
-2-MeC
3
H
4
)(1), prepared in situ by reaction of [Pd(
3
-C
4
H
7
)Cl]
2
with
AgCF
3
SO
3
, with various thionate ligands, gives new polymeric complexes formulated as [Pd(
3
-C
4
H
7
)(RS)]
n
(2) [RS =pyS
(pyridine-2-thionate)], im(Me)S(imidazole-3-methyl-2-thionate) (3), pm(Me)
2
S (pyrimidine-4,6-dimethyl-2-thionate) (4). A solution
of 4 contaminated with KCF
3
SO
3
evolves to give crystals that correspond to a new polymeric species whose X-ray crystal
molecular structure indicates the presence of cationic infinite chains built of trinuclear units, [Pd
3
(
3
-C
4
H
7
)
3
{pm(Me)
2
S}
2
]
+
(5).
Finally, the formation of a mononuclear thionate-containing palladium complex [Pd{pm(Me)
2
S}
2
](6) occurs from a solution of
5 after prolonged periods. An X-ray crystal structure determination indicates a square-planar disposition of two thionate ligands
around the Pd atom. The different complexes were characterized by spectroscopic techniques. © 1999 Elsevier Science S.A. All
rights reserved.
Keywords: Palladium complexes; Thionate; Allyl; Pyridine-4,6-dimethyl-2-thionate; Pyridine-2-thionate; Imidazole-3-methyl-2-
thionate
1. Introduction
Heterocyclic thionates are ligands derived from hete-
rocyclic thiones that contain at least one deprotonated
heterocyclic thioamide group (NCS)
-
(see Chart 1)
[1] and can act as monodentate, chelating and bridging
ligands. The aforementioned systems have been exten-
sively studied in the field of coordination chemistry [2].
After the preparation of the first complex, [Ru-
Cl(pyS)(PPh
3
)
2
] (pyS =pyridine-2-thionate) [3], several
families of thionate-containing late transition metal
complexes have been described, most of which are
regarded as polynuclear species with S,N -bridging lig-
ands, although in recent years other coordinating
modes of these ligands have been established [4]. With
regard to Group 10 metals, several thionate-containing
complexes of palladium have been prepared [5] and, in
(Chart 1)
* Corresponding author. Fax: +34-926-295-318.
E-mail address: aotero@qino-cr.uclm.es (A. Otero)
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII:S0022-328X(99)00021-2