Synthesis of Pd3Tl and Pd6Tl2 complexes based on a trinuclear aryl-palladium(II) complex acting as a metallaligand toward thallium(I) through Tl-arene and Tl-I bonds

Article abstract of DOI:10.1021/ic2007793

The metallaligand [(PdIL₂)₃(C₆Me ₃-1,3,5)] (L₂ = 4,4′-di-tert-butyl-2-2′- bipyridine = tbbpy) reacts with TlOTf to afford the complex [{(PdIL ₂)₃C₆Me₃-1,3,5}Tl]OTf, which exists in the solid state as a 2:1 mixture of monomer and dimer, both showing Tl(I)-I and Tl(I)-η⁶-mesitylene bonds. In solution, only the monomer is observed. Heating of toluene solutions of [(PdIL₂)₃(C ₆Me₃-1,3,5)] affords the dinuclear complex [(PdIL ₂)₂(C₆HMe₃-1,3,5)].

Full text of DOI:10.1021/ic2007793

ARTICLE
pubs.acs.org/IC
Synthesis of Pd Tl and Pd Tl Complexes Based on a Trinuclear
3
6 2
ArylꢀPalladium(II) Complex Acting as a Metallaligand Toward
Thallium(I) Through TlꢀArene and TlꢀI Bonds
,†
†
,†
‡
ꢀ
ꢀ
Jos ꢀe Vicente,* Rashmi V. Shenoy, Eloisa Martinez-Viviente,* and Peter G. Jones
†
ꢀ
ꢀ
ꢀ
Grupo de Quimica Organomet ꢀa lica, Departamento de Quimica Inorg ꢀa nica, Facultad de Quimica, Universidad de Murcia, E-30071,
Murcia, Spain
‡
Institut f €u r Anorganische und Analytische Chemie, Technische Universit €a t Braunschweig, Postfach 3329, 38023, Braunschweig,
Germany
S Supporting Information
b
0
ABSTRACT: The metallaligand [(PdIL ) (C Me -1,3,5)] (L = 4,4 -
2
3
6
3
2
0
di-tert-butyl-2ꢀ2 -bipyridine = tbbpy) reacts with TlOTf to afford the
complex [{(PdIL ) C Me -1,3,5}Tl]OTf, which exists in the solid
2
3
6
3
state as a 2:1 mixture of monomer and dimer, both showing Tl(I)ꢀI
6
and Tl(I)ꢀη -mesitylene bonds. In solution, only the monomer is
observed. Heating of toluene solutions of [(PdIL ) (C Me -1,3,5)]
2
3
6
3
affords the dinuclear complex [(PdIL ) (C HMe -1,3,5)].
2
2
6
3
’
INTRODUCTION
Arylpalladium complexes have been extensively investigated
Scheme 1
because of their involvement in many important CꢀC and
1
Cꢀheteroatom bond-forming reactions. Suitable substituents
2
,3
ortho to Pd(II) may influence the reactivity of these complexes
4,5
or participate in formation of organic compounds. We are trying
to extend this chemistry to 1,3,5-tripalladated benzene derivatives
with substituents ortho to each Pd. Such complexes could have a
huge potential for the Pd-mediated synthesis of organic polycyclic
compounds. This is an almost unexplored field, with only three
publications on 1,3,5-tripalladated arenes, two of them by our
6,7
6ꢀ8
research group. Even with other transition metals there are only
three examples of 1,3,5-trinuclear derivatives (one Mn and two Fe
9
complexes).
Tl(I) is known for its bewildering complexity of coordination
1
0
numbers and geometries, a nonstandard behavior often ascribed
andpromoting reactions suchasligand exchange, cyclopalladation,
insertion of unsaturated molecules, rearrangement processes, or
decomposition reactions. We report here a quite different
2
11
to relativistic effects arising from the 6s lone pair. It is able to
form π complexes with aromatic hydrocarbons, as first proposed
for η -Cp ligands and later for arenes. Although not com-
mon, Tl(I) π-arene complexes are now well documented in the
literature, with both inter- and intramolecular interactions re-
3,4
5
12
13
behavior when trying to replace I by OTf in complex 1.
1
4ꢀ16
ported.
heterobimetallic compounds based on Tl(I)ꢀarene interactions,
as reported here. The closest example is a [Tl {Fe(Cp ) }] com-
However, there is no precedent for polynuclear
’
RESULTS AND DISCUSSION
2
2 3
Synthesis and Crystal Structures of 2 and 2&2. The reaction
15
plex with TlꢀCp interactions.
of complex 1 with 1 equiv of TlOTf in THF (Scheme 1) did not
lead to a substitution product but to the unexpected formation of
an adduct of stoichiometry 1:TlOTf (89% yield). Its X-ray crystal
structure shows two different molecules in the unit cell, the
monomer [{(PdIL ) (C Me -1,3,5)}Tl]OTf (2, Scheme 1 and
In 2001 we published the synthesis of the trinuclear complex
0
0
[
1
(PdIL ) (μ-C Me -1,3,5)] (L = 4,4 -di-tert-butyl-2ꢀ2 -bipyridine,
2
3
6
3
2
6
) (Scheme 1), prepared by oxidative addition of 1,3,5-triiodome-
sitylene to 3 equiv of [Pd(dba) ] (dba = dibenzylideneacetone)
in the presence of L . Very frequently, Tl(I) salts of weakly co-
2
2
3
6
3
2
ordinating anions are used as halide-abstracting agents toward
organopalladium halocomplexes, creating a coordination vacancy
Received: April 15, 2011
Published: June 23, 2011
r 2011 American Chemical Society
7189
dx.doi.org/10.1021/ic2007793
|Inorg. Chem. 2011, 50, 7189–7194

Inorganic Chemistry
ARTICLE
Figure 1. Thermal ellipsoid plot (30% probability level) of 2. Selected
bond lengths (Å) and angles (deg): Tl(1)ꢀC(1) = 3.099(7), Tl(1)ꢀ
C(2) = 3.108(8), Tl(1)ꢀC(3) = 3.153(8), Tl(1)ꢀC(4) = 3.169(8),
Tl(1)ꢀC(5) = 3.174(7), Tl(1)ꢀC(6) = 3.111(8), Tl(1)ꢀI(1) =
Figure 2. Thermal ellipsoid plot (30% probability level) of2&2. Selected
0
bond lengths (Å) and angles (deg): Tl(2)ꢀC(1 ) = 3.047(8), Tl(2)ꢀC-
0
0
0
(
2 ) = 3.101(8), Tl(2)ꢀC(3 ) 3.128(8), Tl(2)ꢀC(4 ) = 3.101(8),
3
.5508(7), Tl(1)ꢀI(2) = 3.6048(7), Tl(1)ꢀI(3) = 3.6261(7), Pd-
0
0
Tl(2)ꢀC(5 ) = 3.081(8), Tl(2)ꢀC(6 ) = 3.038(8), Tl(2)ꢀI(4) =
(
2
(
1)ꢀC(1) = 2.002(8), Pd(1)ꢀN(11) = 2.077(6), Pd(1)ꢀN(21) =
.137(6), Pd(1)ꢀI(1) = 2.5714(8), Pd(2)ꢀC(3) = 1.996(8), Pd(2)ꢀN-
31) = 2.079(7), Pd(2)ꢀN(41) = 2.125(7), Pd(2)ꢀI(2) = 2.5850(8),
Pd(3)ꢀC(5) = 2.010(8), Pd(3)ꢀN(51) = 2.073(6), Pd(3)ꢀN(61) =
.140(6), Pd(3)ꢀI(3) = 2.5625(8), Pd(1)ꢀI(1)ꢀTl(1) = 93.05(2),
3
(
2
(
2
(
9
.4592(7), Tl(2)ꢀI(5) = 3.6203(7), Tl(2)ꢀI(6) = 3.5962(7), Pd-
0
0
0
4)ꢀC(1 ) = 1.989(8), Pd(4)ꢀN(11 ) = 2.069(7), Pd(4)ꢀN(21 ) =
0
.106(7), Pd(4)ꢀI(4) = 2.5821(9), Pd(5)ꢀC(3 ) = 1.992(8), Pd-
0
0
5)ꢀN(31 ) = 2.061(7), Pd(5)ꢀN(41 ) = 2.114(7), Pd(5)ꢀI(5) =
2
0
0
.5654(9), Pd(6)ꢀC(5 ) = 1.996(8), Pd(6)ꢀN(51 ) = 2.065(6), Pd-
Pd(2)ꢀI(2)ꢀTl(1) = 92.91, Pd(3)ꢀI(3)ꢀTl(1) = 93.80(2), C(1)ꢀPd-
0
6)ꢀN(61 ) = 2.117(6), Pd(6)ꢀI(6) = 2.5860(9), Pd(4)ꢀI(4)ꢀTl(2) =
(
(
1)ꢀN(11) = 94.0(3), C(1)ꢀPd(1)ꢀI(1) = 87.9(2), N(11)ꢀPd-
1)ꢀN(21) = 77.8(2), N(21)ꢀPd(1)ꢀI(1) = 100.45(17), C(3)ꢀ
2.29(2), Pd(5)ꢀI(5)ꢀTl(2) = 92.55, Pd(6)ꢀI(6)ꢀTl(2) = 91.27(2),
0
0
0
C(1 )ꢀPd(4)ꢀN(11 ) = 93.0(3), C(1 )ꢀPd(4)ꢀI(4) = 88.1(2),
Pd(2)ꢀN(31) =93.5(3), C(3)ꢀPd(2)ꢀI(2) = 88.0(2), N(31)ꢀPd-
0
0
0
N(11 )ꢀPd(4)ꢀN(21 ) = 78.4(3), N(21 )ꢀPd(4)ꢀI(4) = 100.37(19),
(
(
2)ꢀN(41) = 78.29(3), N(41)ꢀPd(2)ꢀI(2) = 100.05(18), C(5)ꢀPd-
3)ꢀN(51) = 95.3(3), C(5)ꢀPd(3)ꢀI(3) = 87.9(2), N(51)ꢀPd(3)ꢀ
0
0
0
C(3 )ꢀPd(5)ꢀN(31 ) = 94.4(3), C(3 )ꢀPd(5)ꢀI(5) = 87.7(2), N-
0
0
0
(
31 )ꢀPd(5)ꢀN(41 ) = 78.7(3), N(41 )ꢀPd(5)ꢀI(5) = 99.21(19),
N(61) = 77.99(3), N(61)ꢀPd(3)ꢀI(3) = 99.47(18).
0
0
0
C(5 )ꢀPd(6)ꢀN(51 ) = 93.9(3), C(5 )ꢀPd(6)ꢀI(6) = 89.0(2), N-
0
0
0
(
51 )ꢀPd(6)ꢀN(61 ) = 79.3(2), N(61 )ꢀPd(6)ꢀI(6) = 98.92(18).
Figure 1) and the centrosymmetric dimer [{(PdIL ) (C Me -
2
3
6
3
1
,3,5)}Tl] (OTf) (2&2, Scheme 1 and Figure 2). In both
2 2
6
complexes, each Tl atom is η -bonded to one mesitylene ring.
In addition, the Tl atom in 2 is bonded to the three iodo ligands
in a distorted trigonal planar coordination and in 2&2 two
Pd(μ -I)Tl and four Pd(μ -I)Tl bridges are formed. Few
examples have been reported in which a Tl(I) salt reacts with
2.788(2) Å has been reported in a cluster in which thallium is
2
5
bonded only to a triangular Ni moiety and an iodide. The
3
Tlꢀcentroid distances are 2.803 Å in 2 and 2.742 Å for 2&2,
3
2
significantly shorter than those found in other Tl(I) mesitylene
2
26
complexes (TlꢀCt = 2.94ꢀ3.35 Å). Indeed, 2.742 Å is the
second shortest TlꢀCt distance for any Tlꢀarene complex, only
[
M]ꢀX complexes without precipitation of TlX, giving com-
17
16
plexes containing TlꢀXꢀM bonds. Most involve Ru and for all
surpassed by 2.723 Å in Tl(C Me ). The near identity (within
6
6
1
7ꢀ19
X = F or Cl.
These species are formed when the halo ligands
0.002 Å) of the Tlꢀplane and Tlꢀcentroid distances means that
the Tl atoms lie directly over the centers of the rings. The PdꢀI
lengths (2.5625(8)ꢀ2.5860(9) Å) are slightly shorter than those
in 1 (2.5791(4)ꢀ2.5886(4) Å), possibly as a consequence of the
strong Tlꢀmesitylene bond. The TlꢀTl distance in the dimer is
5.422 Å, which excludes any thallophillic interaction, and no
TlꢀO contacts are observed, neither in 2 nor in 2&2.
of mononuclear complexes form bridges with the Tl(I) ions.
3
Only in one case an additional weak η ꢀTlꢀarene contact is
1
9
observed. Therefore, complexes 2 and 2&2 are unprecedented
because (1) they involve the first example in which a trinuclear
metal complex acts as a metallaligand, which, in addition, displays
two different ways in which the metallaligand coordinates to
Tl(I) in the solid state, the monomer 2 and the dimer 2&2, and
Both 2 and 2&2 show somewhat distorted square planar
coordination around the palladium atoms. Mean deviations from
the best plane through Pd and the four donor atoms are in the
range 0.014ꢀ0.097 Å (0.063 Å for Pd1, 0.029 Å for Pd2, and
0.097 Å for Pd3 in 2 and 0.014 Å for Pd4, 0.016 Å for Pd5, and
0.042 Å for Pd6 in 2&2) The nine carbon atoms of the mesityl
ring are coplanar, with mean deviations of only 0.020 (2) and
0.012 Å (2&2). The palladium substituents lie out of this plane
by 0.29 (Pd1), 0.13 (Pd2), and 0.24 (Pd3) Å (2) and 0.16 (Pd4),
0.13 (Pd5), and 0.19 (Pd6) Å (2&2), always in the opposite
direction from the relevant thallium atom. They are arranged
with the PdꢀI vectors approximately perpendicular to the
mesityl plane (maximum deviation 10°). The PdꢀC distances
(
2) Tl(I) coordinates in a fashion that establishes MꢀXꢀTl and
strong Tl(I)ꢀarene bonds.
The TlꢀI distances in 2 and 2&2 (range 3.4592(7)ꢀ3.6261-
(
(
(
7) Å), are shorter than the sum of van der Waals radii
20
3.94 Å) but significantly longer than the sum of covalent radii
2
1
2.84(10) Å). One should however note that Tl(I) is usually
+
ionic and thus resembles the largest alkali metal ion Cs .
Tl(I) I contacts are therefore long (cf. 3.782 and 3.802 Å
3
3 3
ꢀ
22
for Tl(I) ITlI3 in a crown ether complex of Tl(I),
3 3
3
3
.470ꢀ3.696 Å for Tl(I) IC F Au in a goldꢀthallium co-
3 3
3
6 4
2
3
ordination polymer, or 3.36 Å for the shortest Tl(I)ꢀI distance
24
in thallium(I) iodide). An unusually short IꢀTl(I) distance of
7
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Inorganic Chemistry
ARTICLE
Chart 1. Numbering Schemes for Complexes 1 and 2; for 3
the numbering is as for 1, with H instead of [Pd] in
position 4
1
13
Figure 3. Sections of the H, C HMBC spectra of 2 at (a) 298 and (b)
1
3
205
2
13 K, both in CDCl
3
, at 600.13 MHz. 1 Cꢀ Tl couplings are clearly
13
appreciated in the shape of some of the H, C cross-peaks. The vertical
projection is the APT spectrum measured at 298 K.
for 2 and 2&2 are in the range 1.989(8)ꢀ2.010(8) Å, similar to
6
those reported for 1 (1.989(4)ꢀ2.009(4) Å).
The NMR spectra and X-ray crystal structure previously
6
Structure in Solution. NMR Data of Complexes 1 and 2.
When the solid mixture of 2 and 2&2 is dissolved in CDCl or in
reported for 1 reveal a C symmetry (Scheme 1), suggesting
s
hindered rotation of the PdIL moieties around the CꢀPd
3
2
1
6
d -acetone the H NMR spectrum shows a single resonance for
bonds, as only this isomer was detected. However, this rotation
6
all the Me groups of the arene ligands, even at 193 K (in CDCl3).
Consequently, the TlꢀI bridges of 2&2 break in solution to
give complex 2 (which is stable even in a donor solvent such
is necessary for the formation of 2, which has C symmetry. We
hypothesized that the formation of 2 could occur through
undetectable traces of the C3v isomer of 1 in equilibrium with
3v
as d -acetone). The monomeric structure in solution is con-
the C isomer. In an attempt to displace such an equilibrium to
6
s
firmed by ESI-MS (m/z 1827.0) and by PGSE diffusion
the C isomer, we heated d -toluene solutions of 1 up to 90 °C.
s
8
2
7
measurements in CD Cl solutions of complex 1 (for which
What we found instead was the partial decomposition of 1 to give
the dinuclear complex [(PdIL ) (C HMe -1,3,5)] (3). In addi-
2
2
ꢀ
10
2
ꢀ1
D = 7.10 ꢁ 10
m s ) and the mixture of 2 and 2&2 (for
2
2
6
3
ꢀ
10 2 ꢀ1
which D = 7.00 ꢁ 10
m s ). The coordination of Tl to the
tion, no exchange peaks between 1 and any other species were
205
13
8
arene in solution is also reflected in the Tlꢀ C couplings
found in an EXSY experiment at 90 °C in d -toluene, which rules
observed in CDCl for the aryl PdꢀC carbons, C(1), at 298 K
out the supposed C / C equilibrium. Finally, we decided to
3
3v
s
2
(
J
TlC
= 89 Hz) and for both C(1) and C(2) at 213 K (both with
check if removal of Tl from 2 (by reaction with NaI) would afford
the C3v isomer of 1. Surprisingly, we obtained again the Cs
2
205
13
JTlC = 69 Hz, Figure 3). Such Tlꢀ C couplings have been
28
observed in other Tlꢀarene complexes. Therefore, in complex
isomer. Consequently, the rotation of the PdIL group around
2
2
at room temperature the Tl atom is mainly bonded to the
the CꢀPd bond in the 1(C ) f 1(C ) sense is indeed possible
3v
s
CꢀPd carbons of the arene, while at low temperature all CꢀTl
interactions are similar but weaker than TlꢀC(Pd) interactions
at room temperature. Complex 2 in solution has a 3-fold
symmetry axis along the Tlꢀarene bond, with the three [Pd]
moieties being equivalent (as opposed to 1, for which the NMR
resonances appear in a 2:1 pattern because of the different
orientation in the space of one of the [Pd] moieties). A full
which indicates that the C isomer is, probably for steric reasons,
s
at much higher energy than that of the C3v isomer. To explain
that the 1(C ) f 1(C ) isomerization occurs when TlOTf is
s
3v
added to 1, we propose that the complex acts as a chelating ligand
+
toward the Tl ion using the arene π system and the two I ligands
located at the same side; this could modify the environment
around the third PdIL group, allowing its rotation to give 2.
2
1
13
assignment of the H and C resonances of 1 and 2 has been
Synthesis, NMR Data, and X-ray Structure of 3. Complex 3
has been conveniently prepared by heating a toluene solution of
1 for 2 days, followed by chromatographic purification (see
Experimental Section). Its X-ray crystal structure is reproduced
in Figure 4. The two palladium atoms also show slightly distorted
square planar coordination, with mean deviations from the best
plane through Pd and the four donor atoms of 0.024 (Pd1) and
0.017 Å (Pd2). The nine carbon atoms of the mesityl ring are
again coplanar, with a mean deviation of only 0.023 Å, and the
13
achieved (see Experimental Section; the C NMR data of 1 had
not been previously reported). The assignment of the tbbpy
0
protons H16 (δ 8.03ꢀ7.92 ppm) and H16 (δ = 9.48ꢀ9.24
ppm) is based on the NOE cross-peaks found between H16 and
the Me protons of the arene (Chart 1). The H16 protons in 1 and
0
2
are strongly shifted to lower frequencies with respect to H16
and the model complex [PdI (tbbpy) ] [δ (H16) = 9.84 ppm],
2
2
as a consequence of the anisotropic effect of the aryl ring.
7
191
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Inorganic Chemistry
ARTICLE
.405 and 1.404 (s, 9H, tBu or tBu ), 1.400 and 1.388 (s, 18H, tBu or
0
1
0
13
1
0
tBu ). C{ H} NMR (150.9 MHz, CDCl ): δ 162.6 (1C, C14 tbbpy),
3
0
1
1
1
62.5 (2C, C14 tbbpy), 162.2 (1C, C14 tbbpy), 162.1 (2C, C14 tbbpy),
55.9 (2C, C12 tbbpy), 154.9 (1C, C12 tbbpy), 154.5 (1C, C12 tbbpy),
53.9 (2C, C12 tbbpy), 152.3 (2C, CH16 tbbpy), 151.9 (1C, CH16
tbbpy), 151.7 (1C, CH16 tbbpy), 150.4 (2C, CH16 tbbpy), 147.2 (2C,
0
0
0
0
C1ꢀPd), 147.0 (1C, C4ꢀPd), 137.5 (1C, C2 aryl), 136.7 (2C, C3 aryl),
0
1
25.5 (1C, CH15 tbbpy), 123.8 (2C, CH15 tbbpy), 123.43 (2C, CH15
0
tbbpy), 123.37 (1C, CH15 tbbpy), 118.2 (2C, CH13 tbbpy), 117.8
1C, CH13 tbbpy), 117.7 (3C, CH13 tbbpy), 35.63 (1C), 35,56 (2C),
0
(
3
0
5.53 (1C) and 35.52 (2C) (CMe
3
and CMe
3
), 30.69 (2C, Me3), 30.66
(
(
1C, Me2), 30.64 (9C), 30.63 (18C), 30.61 (18C), and 30.59 (9C)
0
CMe and CMe ).
3
3
Synthesis of [{(PdI(tbbpy)) C Me -1,3,5}Tl]OTf (2) and Its
3
6
3
Figure 4. Thermal ellipsoid plot (30% probability level) of 3. Selected
bond lengths (Å) and angles (deg): Pd(1)ꢀC(1) = 1.985(3), Pd(1)ꢀ
N(11) = 2.133(3), Pd(1)ꢀN(21) = 2.082(3), Pd(1)ꢀI(1) = 2.5713(3),
Pd(2)ꢀC(3) = 1.995(3), Pd(2)ꢀN(31) = 2.076(3), Pd(2)ꢀN(41) =
Dimer (2&2). TlOTf (13 mg, 0.036 mmol) was added to a solution of
3
[
1,3,5-μ -C
gassed THF (15 mL) under N
overnight. The mixture was then filtered over Celite, and the re-
sulting orange solution was evaporated to dryness. Et O (15 mL) was
6
Me
3
{PdI(tbbpy)}
3
] (1) (60 mg, 0.036 mmol) in dry de-
, and the resulting suspension was stirred
2
2
.132(3), Pd(2)ꢀI(2) = 2.5907(3), C(1)ꢀPd(1)ꢀN(21) = 91.64(12),
C(1)ꢀPd(1)ꢀI(1) = 90.77(10), N(11)ꢀPd(1)ꢀN(21) = 77.87(11),
2
(
11)ꢀPd(1)ꢀI(1) = 99.71(8), C(3)ꢀPd(2)ꢀN(31) = 93.25(11),
added to precipitate an orange solid, which was filtered off, washed with
Et O (3 ꢁ 5 mL), and dried in vacuo to give a mixture of 2 and 2&2 as
2
C(3)ꢀPd(2)ꢀI(2) = 88.96(9), N(31)ꢀPd(2)ꢀN(41) = 77.99(10),
N(41)ꢀPd(2)ꢀI(2) = 99.66(7).
an orange solid. Yield: 63 mg (89%) Mp: 240ꢀ241 °C. Λ
M
(acetone):
ꢀ1
2
ꢀ1
ꢀ1
1
C
62 Ω cm mol . IR (cm ): ν(SdO), 1030, 1256. Anal. Calcd for
Pd STl: C, 38.91; H 4.13; N 4.25; S, 1.62. Found: C,
38.45; H 3.85; N 4.18; S 1.61. ESI-MS: 2-OTf m/z 1827.0. Single
crystals were grown by slow diffusion of hexane into a CHCl solution of
palladium substituents lie out of this plane by 0.70 (Pd1) and0.30 Å
64
H
81
F
3
I
3
N
6
O
3
3
(
Pd2), in opposite directions. The PdꢀI vectors point to opposite
sides of the central arene ring. While for Pd(2)ꢀI(2) this vector is
within 14° of perpendicular to the mesityl plane, for Pd(1)ꢀI(1)
the corresponding deviation is 21°. The PdꢀC distances of
3
1
0
3
2. H NMR (600 MHz, CDCl ): δ 9.24 (d, 3H, H16 tbbpy, JHH = 6 Hz),
3
4
0
4
8.15 (d, 3H, H13 tbbpy, JHH =2Hz),8.09(d,3H,H13 tbbpy, JHH =2Hz),
.94 (d, 3H, H16 tbbpy, JHH = 6 Hz), 7.52 (dd, 3H, H15 tbbpy, JHH =
Hz, JHH = 2 Hz), 7.41 (dd, 3H, H15 tbbpy, JHH = 6 Hz, JHH = 2 Hz),
3
0
3
7
6
3
(
8
1
.985(3) [Pd(1)ꢀC(1)] and 1.995(3) Å [Pd(2)ꢀC(3)] are
4
3
4
6
similar to those found for 2, 2&2 (see above), and 1. The NMR
0
1
.26 (s, 9H, Me2), 1.47 (s, 27 H, tBu), 1.42 (s, 27 H, tBu ). H NMR
data of 3 in CDCl show that in solution the two [PdI(tbbpy)]
3
6
0
3
600 MHz, d -acetone): 9.21 (d, 3H, H16 tbbpy, JHH = 6 Hz), 8.71 and
moieties are equivalent. Thus, replacement of the third [Pd]
moiety in 1 by a H atom in 3 allows free rotation around the
CꢀPd bonds. Similarly to 1 and 2, the H16 protons in 3 have
been assigned by the NOE with the Me protons of the arene, and
they are shifted to low frequency (δ 7.73 ppm) with respect to
0
4
.62 (d, 3H each, H13 and 13 tbbpy, JHH = 2 Hz), 8.10 (d, 3H, H16
tbbpy, J = 6 Hz), 7.81 and 7.62 (dd, 3H each, H15 and 15 tbbpy,
HH = 6 Hz, JHH = 2 Hz), 3.27 (s, 9H, Me2), 1.48 and 1.43 (s, 27H
each, Bu and Bu ). C{ H} NMR (150.9 MHz, CDCl ): δ 164.6 (3C,
C14 tbbpy), 164.1, (3C, C14 tbbpy), 156.9 (3C, C12 tbbpy), 153.7
3C, C12 tbbpy), 152.4 (br, 3C, CH16 tbbpy), 149.4 (v br, d, JTlC = 87
3
0
HH
3
4
J
t
t
0
13
1
3
0
0
H16 (δ 9.63 ppm) due to the anisotropic effect of the aryl ring.
0
0
1
(
Hz, 3C, C1 aryl), 147.9 (3C, CH16 tbbpy), 143.6 (v br, 3C, C2 aryl),
’
EXPERIMENTAL SECTION
0
1
1
24.4 (3C, CH15 tbbpy), 122.9 (3C, CH15 tbbpy), 121.1 (q, JCF = 332
0
NMR Spectra were recorded on Bruker Avance 400 and 600 spectro-
meters. Chemical shifts are given in ppm (δ) relative to tetramethylsi-
lane, Si(CH
been achieved with the help of 2D NMR experiments (see Chart 1 for
atom numbering). Infrared spectra were recorded on a Perkin-Elmer
Hz, 1C, CF
36.0 (3C, CMe
CMe
3
SO
3
), 120.2 (3C, CH13 tbbpy), 119.1 (3C, CH13 tbbpy),
0
3
), 35.8 (3C, CMe
).
3
), 30.8 (3C, Me2), 30.59 (9C,
1
13
1
13
0
), 30.56 (9C, CMe
Synthesis of [{PdI(tbbpy)} C HMe ] (3). A solution of [1,3,5-μ -
3
3
)
4
( H, C). Assignment of the H and C resonances has
3
3
2
6
3
6 3 3 2 2
C Me {PdI(tbbpy)} ] (1) (125 mg, 0.075 mmol) in CH Cl (10 mL) was
16F-PC-FT spectrometer with Nujol mulls between polyethylene
introduced in a Carius tube, and the solvent was evaporated to dryness. Dry
sheets. Melting points were determined on a Reichert apparatus and
are uncorrected. Elemental analyses were carried out with a Carlo Erba
degassed toluene (15 mL) was then added under N , and the resulting
solution was heated at 90 °C for 2 days. The solution was then evaporated to
2 2
dryness, and the residue was extracted with distilled CH Cl and filtered
2
1
106 microanalyzer. The molar conductivity of 2 was measured for a
ꢀ4
ca. 5 ꢁ 10 M solution in acetone with a Crison MicroCM 2200 con-
ductimeter. The mass spectrum was recorded on a Agilent HPLC/MS
TOF 6220 mass spectrometer. TlOTf was prepared by reaction of
over MgSO . The filterate was evaporated to dryness, and Et O (15 mL)
4
2
was added to precipitate an orange yellow solid, which was filtered off and
washed with Et O. Yield: 54 mg. Preparative TLC was done on silica gel
using a mixture of CH Cl /hexane as eluent. The band with R = 0.56 was
2
Tl
Et
2
CO
O. [1,3,5-μ -C
3
and HO
3
SCF
3
(1:2) in water and recrystallized from acetone/
2
2
f
3
2
6
Me
3
{PdI(tbbpy)}
3
] (1) was prepared as described in
collected, and the product was extracted with acetone (30 mL). Evaporation
6
the literature.
of the acetone and addition of Et O (15 mL) rendered a solid, which was
2
1
NMR data of [{PdI(tbbpy)} (μ -C Me -1,3,5)] (1). H NMR
filtered off, thoroughly washed with Et
yellow solid. Yield: 32 mg (37%) Mp: 235ꢀ237 °C. Anal. Calcd for
Pd : C, 48.19; H 5.21; N 5.00. Found: C, 48.08; H 5.54; N 4.63.
Single crystals were grown by slow evaporation of a toluene solution of 3.
2
O and dried in vacuo to give 3 as a
3
3
6
0
3
3
(
(
7
600 MHz, CDCl ): δ 9.48 (d, 2H, H16 tbbpy, J = 6 Hz), 9.34
d, 1H, H16 tbbpy, JHH = 6 Hz), 8.03 (d, 2H, H16 tbbpy, JHH = 6 Hz),
.93 (d, 1H, H13 tbbpy, JHH = 2 Hz), 7.92 (d, 1H, H16 tbbpy, JHH = 6
3
HH
0
3
3
C
45
H
58
I
2
N
4
2
4
3
0
4
1
0
3
Hz), 7.901 and 7.896 (d, 2H each, H13 and 13 tbbpy, J = 2 Hz), 7.88
H NMR (400 MHz, CDCl ): δ 9.41 (d, 2H, H16 tbbpy, JHH = 6 Hz),
3
HH
0
4
3
3
0
7.94 (d, 2H, J = 2 Hz, H13 tbbpy), 7.91 (d, 2H, J = 2 Hz, H13
HH HH
3
(
J
d, 1H, H13 tbbpy, J = 2 Hz), 7.60 (dd, 1H, H15 tbbpy, J = 6 Hz,
HH = 2 Hz), 7.44 (dd, 2H, H15 tbbpy, JHH = 6 Hz, JHH = 2 Hz), 7.42
HH
HH
4
0
3
4
3
3
tbbpy), 7.73 (d, 2H, H16 tbbpy, JHH = 6 Hz), 7.46 (dd, 2H, JHH = 6 Hz,
0
3
4
4
3
4
0
(dd, 1H, H15 tbbpy, JHH = 6 Hz, JHH = 2 Hz), 7.37 (dd, 2H, H15
J
HH = 2 Hz, H15), 7.44 (dd, 2H, JHH = 6 Hz, JHH = 2 Hz, H15 tbbpy),
3
4
tbbpy, J = 6 Hz, J = 2 Hz), 3.20 (s, 3H, Me2), 3.17 (s, 6H, Me3),
6.47 (s, 1H, aryl CH), 3.11 (s, 3H, Me2), 2.64 (s, 6H, Me3), 1.41 (s, 18H,
HH
HH
7
192
dx.doi.org/10.1021/ic2007793 |Inorg. Chem. 2011, 50, 7189–7194

Inorganic Chemistry
ARTICLE
Table 1. Crystallographic Data for 2 + 2&2 and 3
which the average is given in the text. The differences between these six
D values were always below 2%.
(
2 2
2 + 2&2) 11/2CH Cl 1/
3
3
X-ray Crystallographic Analysis of (2+2&2) 3/2CH Cl
3
2
2
3
complex
2C
6
H
14
7 8
3 2C H
3
1/2C H and 3 2C H . Crystals suitable for X-ray analysis were
6 14 7 8
3
obtained by slow diffusion of n-hexane into a solution of 2 in CHCl
or by slow evaporation of a toluene solution of 3. Crystal data and
refinement details are shown in Table 1. For (2+2&2) 3/2CH Cl
3
formula
fw
68.5 3 3 3 6 3 3 74 2 4
C H91Cl F I N O Pd STl C59H I N Pd
2146.15 (based on the
monomer)
1305.82
3
2
2
3
1
6
/2C H14 a total of 23 7161 reflections were registered to 2θ 52° using
temperature (K)
cryst syst
space group
cell constants
a (Å)
133(2)
100(2)
Mo KR radiation (λ = 0.71073 Å) on a Bruker SMART 1000 CCD
diffractometer. For 3 2C H a total of 220 676 reflections were
monoclinic
monoclinic
P2 /c
3
7
8
P2
1
/c
1
registered to 2θ 56.6° using the same radiation on an Oxford Diffraction
Xcalibur E diffractometer. Both measurements were performed at
low temperature. Absorption corrections were based on multiscans.
21.7626(10)
38.8459(18)
20.8292(9)
90
22.5064(4)
12.0857(2)
22.0979(5)
90
2
29
Structures were refined anisotropically on F using SHELXL-97. For
2+2&2) 11/2CH Cl 1/2C 14, because of the size, the structure
refinement was split into two blocks. The solvent molecules (CH Cl
b (Å)
(
2
2
6
H
3
3
c (Å)
2
2
R (deg)
and hexane) display high U values; two dichloromethanes are disordered.
To improve refinement stability a system of restraints (to disordered
residues and light-atom displacement parameters) was employed. For
3 2C H the two toluene molecules are well ordered.
β (deg)
117.2280
90
109.857(3)
90
γ (deg)
3
volume (Å )
15657.6(12)
8
5653.4
4
7 8
3
Z
ꢀ3
Fcalcd (Mg m
)
1.821
1.534
’ CONCLUSION
ꢀ
1
μ (Mo KR) (mm
F(000)
)
4.095
1.768
We report a series of unprecedented results in the reaction
between a trinuclear halo Pd(II) complex 1 and TlOTf, con-
cerning the nuclearity and nature of the ligands and bonds
involved in the product. The different nature of the species in
the solid state (a mixture of Pd Tl (2) and Pd Tl (2&2) com-
8320
2616
cryst size (mm)
θ range (deg)
no. of reflns coll
0.40 ꢁ 0.10 ꢁ 0.03
1.49ꢀ26.38
237 161
0.2 ꢁ 0.2 ꢁ 0.1
2.23ꢀ28.28
220 676
3
6
2
no. of indep reflns/Rint 31 978/0.1046
transmissions 0.8870 and 0.6004
14 013/0.0589
1.00000 and 0.91015
0/621
plexes with both Tlꢀarene and TlꢀI bonds) and in solution
(
where only the Pd Tl species is present) is derived from X-ray
3
crystallography, NMR, ESI-MS, and PGSE diffusion measure-
ments. Isomerization of the trinuclear Pd(II) complex 1 from Cs
to C3v symmetry in 2 or 2&2 has been investigated, and a
dinuclear Pd(II) complex 3 resulting from thermal decomposi-
tion of 2 has been characterized in solution and in the solid state
by X-ray crystallography.
restraints/parameters 1512/1622
2
goodness-of-fit on F
R1 (I > 2σ(I))
1.014
1.079
0.0490
0.1264
0.0371
wR2 (all reflns)
0.0869
Largest diff. peak/hole 1.956/ꢀ1.575
2.890/ꢀ1.399
ꢀ
3
(
e Å )
3
’
ASSOCIATED CONTENT
0
1
tBu ), 1.38 (s, 18H, tBu). H NMR (400 MHz, d
8
-toluene): δ 9.63 (d, 2H,
S
Supporting Information. CIF files for the crystal struc-
b
0
3
3
H16 tbbpy, J = 6 Hz), 8.10 (d, 2H, H16 tbbpy, J = 6 Hz), 7.48 and
HH
HH
tures. This material is available free of charge via the Internet at
http://pubs.acs.org.
3
0
.45 (d, 2H each, J = 2 Hz, H13 and 13 tbbpy), 7.05 (s, 1H, aryl CH),
HH
7
6
3
3
4
0
.80 and 6.58 (dd, 2H each, JHH = 6 Hz, JHH = 2 Hz, H15 and 15 tbbpy),
.88 (s, 3H, Me2), 3.27 (s, 6H, Me3), 1.01 and 0.91 (s, 18H each, tBu and
tBu ). C{ H} NMR (150.9 MHz, CDCl ): δ 162.8 (2C, C14 tbbpy),
62.6, (2C, C14 tbbpy), 155.5 (2C, C12 tbbpy), 154.2 (2C, C12 tbbpy),
’
AUTHOR INFORMATION
0
13
1
0
0
3
1
1
1
Corresponding Author
*E-mail: jvs1@um.es (J.V.);eloisamv@um.es (E.M.-V.);p.jones@
tu-bs.de (P.G.J.).
0
52.1 (2C, CH16 tbbpy), 150.6 (2C, CH16 tbbpy), 145.2 (2C, C1ꢀPd),
41.9 (1C, C2 aryl), 136.3 (2C, C3 aryl), 127.2 (1C, CH4 aryl), 124.7 (2C,
0
CH15 tbbpy), 123.7 (2C, CH15 tbbpy), 118.1 (2C, CH13 tbbpy), 117.8
2C, CH13 tbbpy), 35.64 (2C, CMe
0
0
), 32.0 (1C,
(
3
), 35.58 (2C, CMe
), 26.2 (2C, Me3).
3
0
Me2), 30.6 (6C, CMe
3
), 30.5 (6C, CMe
3
’ ACKNOWLEDGMENT
Diffusion Measurements. PGSE diffusion measurements on
complexes 1 and 2 were performed on a Bruker AVANCE 600 MHz
spectrometer equipped with a HR Z-gradient BBO probe and using the
standard ledbpgp2s pulse program from Bruker Topspin software (using
a stimulated echo and longitudinal eddy current delay, with bipolar
gradient pulses and two spoiling gradients). Sine-shaped gradients were
used, and measurements were recorded with 16 K time domain data
We thank the Ministerio de Educaci ꢀo n y Ciencia (Spain),
FEDER (Project CTQ2007-60808/BQU), and Fundaci ꢀo n
S ꢀe neca (04539/GERM/06) for financial support. R.V.S. is grateful
to the European Commission for a Marie Curie Individual
Fellowship (IIF).
points in t
2
dimension and 16 t
1
increments, 24 transients for each t
1
’ REFERENCES
increment, and a relaxation delay of 5 s. The gradient length (δ = 2*P30)
was 1.6 ms, and two different measurements with diffusion times Δ
(
1) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.Tsuji, J.
Palladium Reagents and Catalysts; John Wiley: Chichester, U.K., 1995.
Whitcombe, N. J.; Hii, K. K.; Gibson, S. E. Tetrahedron 2001, 57, 7449.
Li, G. Y.; Zheng, G.; Noonan, A. F. J. Org. Chem. 2001, 66, 8677. Littke,
A. F.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 4176. Larock, R. C.; Zeni,
(
D20) = 150 and 100 ms were performed to check reproducibility. The
t
D values were measured following the integral decay of the Me and Bu
resonances. Thus, six D values were obtained for each complex from
7
193
dx.doi.org/10.1021/ic2007793 |Inorg. Chem. 2011, 50, 7189–7194

Inorganic Chemistry
ARTICLE
G. Chem. Rev. 2006, 106, 4644. Heck, R. F. Synlett 2006, 2855.
Buchwald, S. L.; Mauger, C.; Mignani, G.; Scholz, U. Adv. Synth. Catal.
J. M.; Monge, M.; Montiel, M.; Olmos, M. E. Inorg. Chem. 2007,
46, 2953. Schmidbaur, H.; Schier, A. Organometallics 2008, 27, 2361.
Welsch, S.; Lescop, C.; R ꢀe au, R.; Scheer, M. Dalton Trans. 2009, 2683.
Zhu, Z.; Wright, R. J.; Brown, Z. D.; Fox, A. R.; Phillips, A. D.; Richards,
A. F.; Olmstead, M. M.; Power, P. P. Organometallics 2009, 28, 2512.
(15) Sarazin, Y.; Hughes, D. L.; Kaltsoyannis, N.; Wright, J. A.;
Bochmann, M. J. Am. Chem. Soc. 2007, 129, 881.
2
006, 348, 23. Corbet, J. P.; Mignani, G. Chem. Rev. 2006, 106, 2651.
Sergeev, A. G.; Spannenberg, A.; Beller, M. J. Am. Chem. Soc. 2008,
30, 15549. Eichman, C. C.; Stambuli, J. P. J. Org. Chem. 2009, 74, 4005.
1
Hayashi, S.; Yorimitsu, H.; Oshima, K. J. Am. Chem. Soc. 2009, 131, 2052.
Fern ꢀa ndez-Rodr ꢀi guez, M. A.; Hartwig, J. F. J. Org. Chem. 2009, 74, 1663.
Alacid, E.; N ꢀa jera, C. J. Org. Chem. 2009, 74, 2321. Tan, Y.; Hartwig,
J. F. J. Am. Chem. Soc. 2010, 132, 3676. Cho, E. J.; Senecal, T. D.; Kinzel,
T.; Zhang, Y.; Watson, D. A.; Buchwald, S. L. Science 2010, 328, 1679.
(16) Sarazin, Y.; Kaltsoyannis, N.; Wright, J. A.; Bochmann, M.
Organometallics 2007, 26, 1811.
(17) Barthazy, P.; Togni, A.; Mezzetti, A. Organometallics 2001,
20, 3472. Becker, C.; Kieltsch, I.; Broggini, D.; Mezzetti, A. Inorg. Chem.
2003, 42, 8417. Drouin, S. D.; Foucault, H. M.; Yap, G. P. A.; Fogg, D. E.
Organometallics 2004, 23, 2583. Szymczak, N. K.; Han, F.; Tyler, D. R.
Dalton Trans. 2004, 3941. Blake, A. J.; Christie, R. M.; Roberts, Y. V.;
Sullivan, M. J.; Schroder, M.; Yellowlees, L. J. J. Chem. Soc., Chem.
Commun. 1992, 848.
(2) Spencer, J.; Pfeffer, M.; Kyritsakas, N.; Fischer, J. Organometallics
1
1
2
995, 14, 2214. Valk, J. M.; Boersma, J.; van Koten, G. Organometallics
996, 15, 4366. Bosque, R.; Benito, M.; Lopez, C. New J. Chem. 2001,
5, 827. Vicente, J.; Abad, J. A.; Hernandez-Mata, F. S.; Jones, P. G. J. Am.
Chem. Soc. 2002, 124, 3848. Vicente, J.; Chicote, M. T.; Mart ꢀi nez-
Mart ꢀi nez, A. J.; Jones, P. G.; Bautista, D. Organometallics 2008, 27, 3254.
Vicente, J.; Arcas, A.; G ꢀa lvez-L ꢀo pez, M. D.; Juli ꢀa -Hern ꢀa ndez, F.; Bautista,
D.; Jones, P. G. Organometallics 2008, 27, 1582.
(
Arellano, M. C. Organometallics 1996, 15, 1422. Vicente, J.; Abad, J. A.;
Bergs, R.; Ramirez de Arellano, M. C.; Mart ꢀi nez-Viviente, E.; Jones, P. G.
(18) Devic, T.; Batail, P.; Fourmigue, M.; Avarvari, N. Inorg. Chem.
2004, 43, 3136. Davis, K. B.; Harris, T. D.; Castellani, M. P.; Golen, J. A.;
Rheingold, A. L. Organometallics 2007, 26, 4843. Paredes, P.; Diez, J.;
Gamasa, M. P. Organometallics 2008, 27, 2597.
(19) Kunrath, F. A.; Casagrande, O. L.; Toupet, L.; Carpentier, J.-F.
Eur. J. Inorg. Chem. 2004, 2004, 4803.
3) Vicente, J.; Abad, J. A.; Bergs, R.; Jones, P. G.; Ram ꢀi rez de
Organometallics 2000, 19, 5597. Vicente, J.; Abad, J. A.; Rink, B.;
Hern ꢀa ndez, F.-S.; Ram ꢀi rez de Arellano, M. C. Organometallics 1997,
(20) Bondi, A. J. Phys. Chem. 1964, 68, 441.
(21) Cordero, B.; G ꢀo mez, V.; Platero-Prats, A. E.; Rev ꢀe s, M.; Echeverr ꢀi a,
16, 5269. Vicente, J.; Abad, J. A.; F o€ rtsch, W.; Jones, P. G.; Fischer, A.
Organometallics 2001, 20, 2704. Vicente, J.; Abad, J. A.; Hern ꢀa ndez-
J.; Cremades, E.; Barrag ꢀa n, F.; Alvarez, S. Dalton Trans. 2008, 2832.
(22) Mudring, A.-V.; Rieger, F. Inorg. Chem. 2005, 44, 6240.
(23) Fern ꢀa ndez, E. J.; Laguna, A.; Lasanta, T.; L ꢀo pez-de-Luzuriaga,
J. M.; Montiel, M.; Olmos, M. E. Organometallics 2008, 27, 2971.
(24) Quoted in A. F. Wells, Structural Inorganic Chemistry; Clarendon
Press: Oxford, U.K., 1984.
Mata, F. S.; Rink, B.; Jones, P. G.; Ram ꢀi rez de Arellano, M. C.
Organometallics 2004, 23, 1292. Vicente, J.; Saura-Llamas, I.; Turp ꢀi n, J.;
Ram ꢀi rez de Arellano, M. C.; Jones, P. G. Organometallics 1999, 18, 2683.
Vicente, J.; Abad, J. A.; Frankland, A. D.; Ram ꢀi rez de Arellano, M. C.
Chem.—Eur. J. 1999, 5, 3066. Vicente, J.; Abad, J. A.; Frankland, A. D.;
Lopez-Serrano, J.; Ramirez de Arellano, M. C.; Jones, P. G. Organome-
tallics 2002, 21, 272. Vicente, J.; Abad, J. A.; L ꢀo pez-S ꢀa ez, M. J.; F €o rtsch,
W.; Jones, P. G. Organometallics 2004, 23, 4414. Vicente, J.; Abad, J. A.;
L ꢀo pez-S ꢀa ez, M. J.; Jones, P. G. Organometallics 2006, 25, 1851.
(25) Johnson, M. J. A.; Gantzel, P. K.; Kubiak, C. P. Organometallics
2002, 21, 3831.
(26) Noirot, M. D.; Anderson, O. P.; Strauss, S. H. Inorg. Chem.
1987, 26, 2216. Strauss, S. H.; Noirot, M. D.; Anderson, O. P. Inorg.
Chem. 1986, 25, 3850. Schmidbaur, H.; Bublak, W.; Riede, J.; M €u ller, G.
Angew. Chem., Int. Ed. Engl. 1985, 24, 414. Frank, W.; Korrell, G.; Reiss,
G. J. Z. Anorg. Allg. Chem. 1995, 621, 765. Frank, W.; Korrell, G.; Reiss,
G. J. J. Organomet. Chem. 1996, 506, 293. Wright, R. J.; Brynda, M.;
Power, P. P. Inorg. Chem. 2005, 44, 3368.
(4) Vicente, J.; Abad, J. A.; Gil-Rubio, J. Organometallics 1996,
15, 3509. Vicente, J.; Abad, J. A.; L ꢀo pez-Serrano, J.; Jones, P. G.
Organometallics 2004, 23, 4711. Vicente, J.; Abad, J. A.; Shaw, K. F.;
Gil-Rubio, J.; Ram ꢀi rez de Arellano, M. C.; Jones, P. G. Organometallics
1
997, 16, 4557. Vicente, J.; Abad, J.-A.; L ꢀo pez-Serrano, J.; Jones, P. G.;
N ꢀa jera, C.; Botella-Segura, L. Organometallics 2005, 24, 5044. Vicente, J.;
(27) Price, W. S. Annu. Rep. NMR Spectrosc. 1996, 32, 51. Pregosin,
P.; Kumar, P. G. A.; Fernandez, I. Chem. Rev. 2005, 105, 2977.
(28) Schumann, H.; Kucht, H.; Dietrich, A.; Esser, L. Chem. Ber.
1990, 123, 1811. Kunze, A.; Gleiter, R.; Bethke, S.; Rominger, F.
Organometallics 2006, 25, 4787.
Saura-Llamas, I.; Garc ꢀi a-L ꢀo pez, J.-A.; Calmuschi-Cula, B.; Bautista, D.
Organometallics 2007, 26, 2768. Vicente, J.; Saura-Llamas, I.; Garc ꢀi a-
L ꢀo pez, J.-A.; Bautista, D. Organometallics 2009, 28, 448.
(
5) Catellani, M.; Motti, E.; Ghelli, S. Chem. Commun. 2000, 2003.
Vicente, J.; Abad, J. A.; Mart ꢀi nez-Viviente, E.; Ram ꢀi rez de Arellano,
M. C.; Jones, P. G. Organometallics 2000, 19, 752. Vicente, J.; Saura-
(29) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112.
Llamas, I.; Gr €u nwald, C.; Alcaraz, C.; Jones, P. G.; Bautista, D.
Organometallics 2002, 21, 3587. Vicente, J.; Abad, J. A.; L ꢀo pez-Pel ꢀa ez,
B.; Mart ꢀi nez-Viviente, E. Organometallics 2002, 21, 58. Vicente, J.; Saura-
Llamas, I. Comments Inorg. Chem. 2007, 28, 39. Sirlin, C.; Chengebroyen,
J.; Konrath, R.; Ebeling, G.; Raad, I.; Dupont, J.; Paschaki, M.; Kotzyba-
Hibert, F.; Harf-Monteil, C.; Pfeffer, M. Eur. J. Org. Chem. 2004, 1724.
(
6) Vicente, J.; Lyakhovych, M.; Bautista, D.; Jones, P. G. Organo-
metallics 2001, 20, 4695.
7) Vicente, J.; Shenoy, R. V.; Mart ꢀi nez-Viviente, E.; Jones, P. G.
Organometallics 2009, 28, 6101.
(
(8) Sumby, C. J.; Steel, P. J. Organometallics 2003, 22, 2358.
(9) Hunter, D. J. B.; Szigety, A. B. Organometallics 1989, 8, 2670.
Hunter, A. D. Organometallics 1989, 8, 1118. Hunter, A. D.; McLernon,
J. L. Organometallics 1989, 8, 2679. Artamkina, G. A.; Beletskaya, I. P.
Mendeleev Commun. 2003, 13, 43. Artamkina, G. A.; Shilova, E. A.;
Shtern, M. M.; Beletskaya, I. P. Russ. J. Org. Chem. 2003, 39, 1282.
(
(
(
(
(
10) Akhbari, K.; Morsali, A. Coord. Chem. Rev. 2010, 254, 1977.
11) Wiesbrock, F.; Schmidbaur, H. J. Am. Chem. Soc. 2003, 125, 3622.
12) Meister, H. Angew. Chem. 1957, 69, 533.
13) Auel, T.; Amma, E. L. J. Am. Chem. Soc. 1968, 90, 5941.
14) Janiak, C. Coord. Chem. Rev. 1997, 163, 107. Gade, L. H. Dalton
Trans. 2003, 267. Fern ꢀa ndez, E. J.; Laguna, A.; L ꢀo pez-de-Luzuriaga,
7
194
dx.doi.org/10.1021/ic2007793 |Inorg. Chem. 2011, 50, 7189–7194