Polyhedron 20 (2001) 3119 – 3125
Allyl – palladium compounds with fluorinated benzenethiolate
ligands. X-ray crystal structure of
[(
3
-C
3
H
5
)Pd(-SC
6
H
4
F-4)
2
Pd(
3
-C
3
H
5
)]
Rocı ´o Redo ´n
a
, Roger Cramer
b
, Sylvain Berne `s
c
, David Morales
d
, Hugo Torrens
a,
*
a
DEPg, Facultad de Quı ´mica, UNAM, Cd. Uniersitaria, 04510 Mexico City, D.F., Mexico
b
Department of Chemistry, Uniersity of Hawai’i at Ma ¯noa, 2545 McCarthy Mall, Honolulu, HI 96822 -2275, USA
c
Centro de Quı ´mica, IC-UAP, Bld. 14 Sur 6303, San Manuel, 72570 Puebla Pue., Mexico
d
Instituto de Quı ´mica, UNAM. Cd. Uniersitaria, 04510 Mexico City, D.F., Mexico
Received 25 October 2000; accepted 21 August 2001
Abstract
Treatment of the di--chloride allyl – palladium complex [(
3
-C
3
H
5
)Pd(-Cl)
2
Pd(
3
-C
3
H
5
)] with Pb(SR)
2
in acetone affords
dinuclear fluorothiolate bridged complexes of the type [(
3
-C
3
H
5
)Pd(-SR)
2
Pd(
3
-C
3
H
5
)] (R =C
6
F
5
, 1;C
6
HF
4
-4, 2;C
6
H
4
F-2, 3;
C
6
H
4
F-3, 4 and C
6
H
4
F-4, 5). Complex 1 reacts with para -substituted phosphines P(C
6
H
4
X-4)
3
to give the mononuclear
perfluorobenzenethiolate complexes [Pd(SC
6
F
5
)(
3
-C
3
H
5
)(P(C
6
H
4
X-4)
3
)] (X =F, 6; CF
3
, 7; OCH
3
, 8 and CH
3
, 9). The single
crystal X-ray diffraction structure of [(
3
-C
3
H
5
)Pd(-SC
6
H
4
F-4)
2
Pd(
3
-C
3
H
5
)] (5) has been resolved. © 2001 Published by
Elsevier Science Ltd.
Keywords: Palladium; Fluorothiolate; Allyl; NMR spectroscopy; Crystal structures
www.elsevier.com/locate/poly
1. Introduction
The role of
3
-allyl – palladium compounds in several
palladium-catalysed organic syntheses is now well es-
tablished [1]. Reviews focused on reactions such as
carbonyl allylation [2], carbonylation [3], allyl alkyla-
tion [4], decarbopalladation [5] or on their application
as enantioselective homogeneous catalysts [6] have been
published.
In contrast with other derivatives of allyl – palladium
complexes [1], those bearing sulfur-containing ligands
are relatively scarce [7 – 11], even though species with
the fragment [Pd(SR)(
3
-allyl)] are potential precursors
of compounds with an organic-SR skeleton and, in-
deed, [Pd(SR)(
3
-allyl-R)L] affords RCHCHCH
2
SR
[9].
As part of our continued interest in dinuclear com-
pounds with fluoroarylthiolato bridging units [12], we
have studied a series of allyl – palladium dinuclear com-
plexes, [(
3
-C
3
H
5
)Pd(-SR)
2
Pd(
3
-C
3
H
5
)] (R =fluori-
nated substituents), and the reactivity of [(
3
-C
3
H
5
)-
Pd(-SC
6
F
5
)
2
Pd(
3
-C
3
H
5
)] towards para -substituted
phosphines. To the best of our knowledge, fluorothio-
late-containing derivatives of allyl complexes are repre-
sented by a single example: [(
3
-C
3
H
5
)Ni(-SC
6
F
5
)
2
-
Ni(
3
-C
3
H
5
)] [10].
In this paper we discuss the synthesis and properties
of [(
3
-C
3
H
5
)Pd(-SR)
2
Pd(
3
-C
3
H
5
)] (R =C
6
F
5
, 1;
C
6
HF
4
-4, 2;C
6
H
4
F-2, 3;C
6
H
4
F-3, 4 and C
6
H
4
F-4, 5)
and [Pd(SC
6
F
5
)(
3
-C
3
H
5
)(P(C
6
H
4
X-4)
3
)] (X =F, 6;
CF
3
, 7; OCH
3
, 8 and CH
3
9) and the single crystal
X-ray diffraction structure of compound 5.
2. Experimental
All manipulations were carried out under dry, oxy-
gen-free dinitrogen atmospheres using standard vacuum
and Schlenk-tube techniques.
Solvents were dried and degassed using standard
techniques [13], and thin layer chromatography (TLC)
* Corresponding author. Tel./fax: +52-5-622-3724.
E-mail address: torrens@servidor.unam.mx (H. Torrens).
0277-5387/01/$ - see front matter © 2001 Published by Elsevier Science Ltd.
PII:S0277-5387(01)00934-2