The substitution of arene by alkenes in linear trinuclear palladium complex Pd3(NO)2(μ-CF3CO2) 4(η2-C6H5CH3) 2. X-ray structure of Pd3(NO)2(μ-CF 3CO2)4(η2-CH2CHPh) 2

Article abstract of DOI:10.1016/j.jorganchem.2010.05.019

An interaction of Pd₃(NO)₂(μ-CF₃CO ₂)₄(η²-C₆H₅Me) ₂ (I) with alkenes has been studied. A replacement of η²-coordinated arene by various olefins has been found to result in complexes of different nuclearity, Pd₃(NO)₂(μ- CF₃CO₂)₄(η²-L)₂ (L = Me₃CCHCH₂ (III), CH₂CHPh (IV)), Pd ₄(μ-NO)₂(μ-CF₃CO₂) ₄(η²-CH₂CHPh)₄ (V). Complexes IV and V have been characterized by an X-ray diffraction analysis. Molecule IV is constituted of a linear trinuclear metal core bearing η²- coordinated molecules of styrene, terminal nitrosyl and bridging carboxylate groups, whereas, complex V has a tetrahedral core, with η²- coordinated styrene molecules and half-bridging nitrosyl and carboxylate groups. Complex V represents a new type of nitrosyl carboxylate tetrahedral palladium cluster. The substitution of arene molecules by alkenes in trinuclear Pd ₃(NO)₂(μ-CF₃CO₂) ₄(η²-C₆H₅Me)₂ was investigated. The process results in a formation of linear complexes Pd ₃(NO)₂(μ-CF₃CO₂) ₄(η²-L)₂ (L = trans-stylbene, neohexene, styrene) and tetrahedral clusters Pd₄(μ-NO)₂(μ- CF₃CO₂)₄(η²-L)₄ (L = styrene). The latter is a first example of nitrosyl carboxylate complex with tetrahedral metal core.

Full text of DOI:10.1016/j.jorganchem.2010.05.019

Journal of Organometallic Chemistry 695 (2010) 2083e2088
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
The substitution of arene by alkenes in linear trinuclear palladium complex
Pd3(NO)2(
Pd3(NO)2(
m
m
-CF3CO2)4(
-CF3CO2)4(
h
h
2-C6H5CH3)2. X-ray structure of
2-CH2CHPh)2 and Pd4( 2-CH2CHPh)4
m-NO)2(m-CF3CO2)4(h
,
b
,
a,
Roman E. Podobedov a , Tatiana A. Stromnova b, Andrei V. Churakova, Lyudmila G. Kuzmina a,
*
Inessa A. Efimenko a
a N. S. Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, 31 Leninsky prosp., 119991 Moscow, Russian Federation
b M. V. Lomonosov Moscow State Academy of Fine Chemical Technology, 86 prosp. Vernadskogo, 119571 Moscow, Russian Federation
a r t i c l e i n f o
a b s t r a c t
An interaction of Pd3(NO)2(m-CF3CO2)4(h
2-C6H5Me)2 (I) with alkenes has been studied. A replacement of
Article history:
h
2-coordinated arene by various olefins has been found to result in complexes of different nuclearity,
Received 7 April 2010
Received in revised form
11 May 2010
Accepted 16 May 2010
Available online 24 May 2010
Pd3(NO)2(
CH2CHPh)4 (V). Complexes IV and V have been characterized by an X-ray diffraction analysis. Molecule IV
is constituted of a linear trinuclear metal core bearing
2-coordinated molecules of styrene, terminal
nitrosyl and bridging carboxylate groups, whereas, complex V has a tetrahedral core, with
2-coordi-
m
-CF3CO2)4(
h
2-L)2 (L
¼
Me3CCH]CH2 (III), CH2CHPh (IV)), Pd4(m-NO)2(m -
-CF3CO2)4(h2
h
h
nated styrene molecules and half-bridging nitrosyl and carboxylate groups. Complex V represents a new
type of nitrosyl carboxylate tetrahedral palladium cluster.
Keywords:
Palladium cluster
Nitrosyl carboxylate
Alkene
Ó 2010 Elsevier B.V. All rights reserved.
Substitution of arene
X-ray structure
1. Introduction
The palladium complexes earlier synthesized by us, with h2
coordinated arene molecule [5e7] belong to the second group.
-
Complexes of transition metals containing
benzene molecule or its derivatives are widely known, whereas, the
examples of complexes with
arenes are few in number. Only several palladium complexes of this
kind that may be divided into two groups are described.
The first group consists of the complexes with PdePd unit
sandwiched between two arene molecules. These dimeric
complexes have a total composition Pd2(arene)2X2, with the
anionic ligands occupying the axial positions. In the case when the
PdePd bond is parallel to the planes of arene rings, each of the Pd
atoms is bounded to three carbon atoms of both arene rings
(arene ¼ benzene, X ¼ Al2Cl7) [1,2]. In the case when the PdePd
bond is non-parallel to the planes of arene rings, each Pd atom is
bounded to two or three carbon atoms of each arene ring
(arene ¼ benzene, X ¼ GaCl4, Ga2Cl7 or GaBr4; arene ¼ toluene,
X ¼ GaCl4 or GaBr4; arene ¼ p-xylene, X ¼ GaCl4 or GaBr4) [3,4].
h
6-coordinated
These substances are of the common composition Pd3(NO)2(m-
RCO2)4(
h
2-arene)2 (R ¼ CF3, arene ¼ toluene (I), R ¼ CCl3,
h
2- or 3-coordinated molecule of
h
arene ¼ benzene (II)). Both molecules have a trinuclear linear metal
core, with the PdePdePd angle equal to 180ꢀ in I and II (Fig. 1).
The arene molecules are linked to each terminal Pd atoms
through a couple of carbon atoms. The plane of each arene mole-
cule is perpendicular to the nearest Pde(OC(R)O)2ePd plane. Two
PdeC bonds are nearly equal (average distance is 2.417 Å for I and
2.420 Å for II). The rest of the PdeC distances with the arene
molecules are much longer and vary within 3.096e3.691 Å for I and
3.175e3.732 Å for II. Therefore, the coordination of arene molecules
R
C
R
C
O
O O
Pd
O
ON
X
Pd
Pd
X
NO
O
O O
O
C
R
C
R
* Corresponding author. N. S. Kurnakov Institute of General and Inorganic
Chemistry of the Russian Academy of Sciences, 31 Leninsky prosp., 119991 Moscow,
Russian Federation. Tel.: þ7 4959554844; fax: þ7 4959541279.
E-mail address: bambryounger@gmail.com (R.E. Podobedov).
Fig. 1. Structure of complexes I (R ¼ CF3, X ¼ Me) and II (R ¼ CCl3, X ¼ H).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.05.019

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R.E. Podobedov et al. / Journal of Organometallic Chemistry 695 (2010) 2083e2088
Fig. 2. The molecular structure of IV. Only one independent molecule is presented. Hydrogen atoms are omitted for clarity. Displacement ellipsoids are shown at the 50% probability
level. Dashed lines denote short intramolecular Pd.Pd contacts (3.0195(5) and 3.1686(5) Å).
is best described as
h
2 type interaction. The phenyl rings are planar
case of propylene) in solution were recorded by the GCeMS
(together with vinyltrifluoroacetate and allyltrifluoroacetate). Our
attempts to separate any Pd-containing compounds from the reac-
tion mixtures failed.
and shown no significant elongations of the coordinated CeC bond.
It was found that in complex I, the coordinated toluene molecule is
not replaced even on recrystallization from non-aromatic solvents.
Unlike complex I, complex II decomposes under the same condi-
tions. Thus the Pd(m-RCO2)2Pd(m-RCO2)2Pd fragment in complex I is
2.2. Reaction of I with neohexene (3,3-dimethyl-1-butene)
stable enough to remain under conditions of the replacement of h2
-
coordinated toluene molecule to another ligand.
This Pd3-fragment is a well-known building block for a design of
oligomeric palladium carboxylate complexes. In these complexes
An addition of solution of neohexene in CH2Cl2 to the solution of
I in CH2Cl2 leads to the formation of a new complex of the
composition Pd3(NO)2(CF3CO2)4(Me3CCH]CH2)2 (III). The IR
three palladium atoms form a Pd(m-RCO2)2Pd(m-RCO2)2Pd chain
spectrum of III displays the presence of terminal NO-groups (
n
(NO) ¼ 1680 cmꢁ1). This value is significantly lower than that in I
(1730 cmꢁ1), apparently, due to the higher electron donor capa-
bility of neohexene as compared with that of toluene. The 1H NMR
(R ¼ Me, CCl3, CF3), in which the terminal palladium atoms are
coordinatedbyancillaryligands.Insuchlinearmolecules, adistortion
of the square-planar coordination around the central metal atom is
far less pronounced than in the complexes with the bent metal chain.
Onlya fewcompounds with the linear metal chain are known [8]. The
PdePd distances in these compounds range within 2.86e3.08 Å
dependingonthe nature of thesubstituentR in thecarboxylategroup
and the ancillary ligand. In this paper we report interactions of tri-
nuclear palladium carboxylate complex I with alkenes.
spectrum of III contains singlet (
group, doublet (
¼ 5.90 ppm, Me3CCH]CH2).
d
¼ 1.13 ppm) from protons of tBu-
d
¼ 4.90 ppm, Me3CCH]CH2), and multiplet
(d
2.3. Reaction of I with styrene
The first stage of the interaction of styrene with I is analogous to
the reaction with neohexene. It results in fast (for 1 h) formation of
a new complex Pd3(NO)2(CF3CO2)4(CH2CHPh)2 (IV). As in the case
of complex I, the IR spectrum of IV contains the band at 1720 cmꢁ1
attributed to the terminal NO-groups.
2. Results and discussion
2.1. Reaction of I with ethylene and propylene
A treatment of I in CH2Cl2 solutionwith ethylene or propylene for
some hours at ambient temperature leads to the complete decom-
position of I to palladium black. The products of alkene oxidation
(acetaldehyde in the case of ethylene and propionaldehyde in the
The structure of IV was confirmed by the X-ray diffraction
analysis (see Fig. 2). The asymmetric unit contains two crystallo-
graphically independent molecules with the close geometric
parameters. The molecules are situated at the symmetry centres and

R.E. Podobedov et al. / Journal of Organometallic Chemistry 695 (2010) 2083e2088
2085
Table 1
Selected bond lengths (Å) and angles (ꢀ) for IV.a
CF3
C
CF3
C
Pd(1)ePd(2)
Pd(2)eO(12)
Pd(2)eO(22)
Pd(1)eO(11)
Pd(1)eO(21)
Pd(1)eC(13)
Pd(1)eC(14)
Pd(1)eN(1)
C(13)eC(14)
C(14)eC(15)
N(1)eO(1)
3.0195(5)
1.995(3)
2.012(3)
2.285(3)
2.210(3)
2.232(5)
2.381(5)
1.938(5)
1.362(7)
1.478(7)
1.147(7)
Pd(3)ePd(4)
Pd(3)eO(31)
Pd(3)eO(41)
Pd(4)eO(32)
Pd(4)-O(42)
Pd(3)eC(33)
Pd(3)eC(34)
Pd(3)eN(2)
3.1686(5)
2.248(3)
2.265(3)
1.997(3)
2.000(3)
2.221(5)
2.343(5)
1.910(5)
1.353(7)
1.473(7)
1.068(9)
1.129(13)
132.9(6)
118.8(8)
126.0(5)
L
O
O O
Pd
O
ON
L
I
Pd
Pd
CH2Cl2
NO
L
O
O O
O
C
C
CF3
CF3
C(33)eC(34)
C(34)eC(35)
N(2)eO(3)b
L = PhCH=CH2; Me3CCH=CH2
N(2)eO(4)b
Scheme 1. Interaction I with alkenes.
Pd(1)eN(1)eO(1)
112.8(5)
126.6(5)
Pd(3)eN(2)eO(3)b
Pd(3)eN(2)eO(4)b
C(33)eC(34)eC(35)
angles varying within a narrow range 88.6(1)e91.4(1)ꢀ(Table 1). To
the best of our knowledge, the linear arrangement of three Pd atoms
is rather rare. This was previously observed in a few palladium
C(13)eC(14)eC(15)
a
Two independent molecules.
Major and minor components of disorder.
b
carboxylates I [6], [Pd3(
[Pd3( -OCOCH3)4(C6H3Me2)2(S(CH2CHMe2)2)2] [11].
The Pd2( -RCO2) fragments are planar within 0.229(2) Å. The CF3
m-OCOCH3)4(h
3-C3H(COOCMe3)2)] [10], and
m
have strictly linear trinuclear metal core. Both terminal Pd atoms are
linked to the central one by a couple of bridging carboxylate ligands.
Two Pde(OC(R)O)2ePd fragments are virtually orthogonal. The
PdePd distances are equal to 3.0195(5) and 3.1686(5) Å. These
m
groups in three of four carboxylate ligands display a high level of the
rotational disorder. Each terminal Pd atom bears a terminal NO-
group and p-coordinated styrene molecule. The PdeNeO angles lie
within 112.8(5)e132.9(6)ꢀ in two independent molecules, which
corresponds to the sp2 hybridization of nitrogen atom. Therefore,
the NO ligands present the monoanionic form. The PhCaH]CbH2
values lie within the range 2.821e3.428 Å reported for Pd2(m-RCO2)2
units in the Cambridge Structural Database [9] (ver. 5.30, 156
refcodes, 243 fragments). In both molecules, the central Pd atom has
a square-planar coordination environment, with the OePdeO
double bonds of the nearly planar styrene molecules are h
2-bonded
Fig. 3. The chains in the structure of IV formed by intermolecular Pd.Pd interactions. Fluorine and hydrogen atoms are omitted for clarity.

2086
R.E. Podobedov et al. / Journal of Organometallic Chemistry 695 (2010) 2083e2088
Fig. 4. The molecular structure of V. Hydrogen atoms is omitted for clarity. Displacement ellipsoids are shown at the 50% probability level.
to the Pd atoms. A significant difference in PdeCa and PdeCb
distances was observed (2.232(5), 2.221(5) vs 2.381(5), 2.343(5) Å,
respectively). The metal coordination resulted in a noticeable
elongation of the C]C bonds (1.353(7) and 1.362(7) Å) in compar-
ison to the value found in crystalline styrene (1.325(2) Å) [12] .
Within the molecule, two styrene ligands possess transoid mutual
arrangement [6]. The cluster has a total electron count of 48 elec-
trons (¼10 ꢂ 3 (Pd) þ 3 ꢂ 4 (carboxylate) þ 1 ꢂ 2 (nitrosyl) þ 2 ꢂ 2
(styrene); monoanionic terminal nitrosyls are considered as 1
electron donors). This corresponds to the 3-Pd 16-e cluster without
any metalemetal bonds.
In contrast to well-known the extended metal atom chain
complexes (EMACs) of Ni [13,14] and Co [15,16], the terminal
palladium atoms in IV do not bear any axial ligands. Thus, the
terminal Pd atoms may form additional intermolecular contacts.
Actually, in crystal of IV, the adjacent molecules are combined into
chains spread along the cell diagonal by weak Pd.Pd interactions
(3.3490(6) Å) (Fig. 3). Thus, the first step of the interaction of I with
alkenes (neohexene, styrene) completely suits (Scheme 1).
However, after crystals of IV were separated, the residual reaction
mixture was concentrated (up to the oil formation) and kept in a fridge.
Two days later, the black crystals formed. Their elemental analysis was
C6H5CH]CH2), quadruplet (
d
¼ 6.73 ppm, C6H5CH]CH2), and multi-
plet (
d
¼ 7.42 ppm, C6H5CH]CH2) were observed. In comparison with
the free styrene molecule, all the signals in Vareshiftedby0.1e0.2 ppm
to the low field, which confirms the coordination of styrene molecule.
Table 2
Selected bond lengths (Å) and angles (ꢀ) for V.
Pd(1)eN(2)
Pd(2)eN(2)
N(2)eO(2)
1.883(4)
1.889(4)
1.173(5)
2.9894(4)
2.7594(4)
2.8495(4)
2.081(3)
2.065(3)
2.088(3)
2.060(3)
2.341(4)
2.319(4)
2.314(4)
2.368(4)
1.358(6)
1.347(7)
1.358(7)
1.362(7)
104.84(17)
128.1(3)
127.1(3)
125.1(4)
126.8(5)
Pd(3)eN(1)
1.878(4)
1.892(4)
1.177(5)
2.9859(4)
2.7084(4)
2.8320(4)
2.420(3)
2.507(3)
2.402(3)
2.554(3)
2.457(4)
2.455(4)
2.444(4)
2.466(4)
1.473(6)
1.474(6)
1.470(7)
1.464(6)
104.75(18)
128.2(3)
126.8(3)
125.7(4)
124.2(4)
Pd(4)eN(1)
N(1)eO(1)
Pd(1)ePd(2)
Pd(1)ePd(3)
Pd(1)ePd(4)
Pd(3)eO(11)
Pd(2)eO(21)
Pd(1)eO(31)
Pd(4)eO(41)
Pd(3)eC(13)
Pd(2)eC(23)
Pd(4)eC(33)
Pd(1)eC(43)
C(13)eC(14)
C(23)eC(24)
C(33)eC(34)
C(43)eC(44)
Pd(1)eN(2)ePd(2)
O(2)eN(2)ePd(1)
O(2)eN(2)ePd(2)
C(13)eC(14)eC(15)
C(23)eC(24)eC(25)
Pd(3)ePd(4)
Pd(2)ePd(4)
Pd(2)ePd(3)
Pd(1)eO(12)
Pd(4)eO(22)
Pd(3)eO(32)
Pd(2)eO(42)
Pd(3)eC(14)
Pd(2)eC(24)
Pd(4)eC(34)
Pd(1)eC(44)
C(14)eC(15)
C(24)eC(25)
C(34)eC(35)
C(44)eC(45)
Pd(3)eN(1)ePd(4)
O(1)eN(1)ePd(3)
O(1)eN(1)ePd(4)
C(33)eC(34)eC(35)
C(43)eC(44)eC(45)
in
a good agreement with the total composition [Pd2(NO)
(CF3CO2)2(CH2CHPh)2]n (V). The IR spectrum of V does not contain the
band at 1650e1730 cmꢁ1 attributed to the terminal NO-group, but
contains the band 1544 cmꢁ1 (NO) for bridging group). In the 1HNMR
(n
spectrum of V, two symmetrical doublets (
d
¼ 5.28 and 5.80 ppm,

R.E. Podobedov et al. / Journal of Organometallic Chemistry 695 (2010) 2083e2088
2087
Ph
HC
CF3OCO
CH2
Pd
NO
CF3OCO
CF3
C
Ph
O
Ph
CH
O
PhCHCH2
CH2Cl2
IV
Pd
CF3
C
CH
HC
Ph
HC
CH
Pd
O
O
O
ON
O
NO
CH2
C
Pd
Pd
CF3
V
F3C
H2C
Ph
CH
CH
O
C
O
O
C
O
Ph
Pd
ON
CF3
CH
O
Pd
HC
CH
Ph
O
C
CF3
Scheme 2. Possible steps formation of cluster V.
The structure of V was determined by the X-ray diffraction anal-
ysis (Fig. 4). In V, the central metal core represents the tetrahedron
with the PdePd distances varying within the range 2.7084(4)e
2.9894(4) Å. Two opposite edged of this tetrahedron are occupied by
nearly symmetrical bridging NO ligands. The PdeN bond lengths
(1.878(4)e1.892(4) Å) are somewhat shorter than those we have
earlier found for the square-planar complex Pd4(NO)2(tBuCO2)6
(1.903(6)e1.917(6) Å) [5]. The two other edges of Pd4 polyhedron are
engaged by four nonsymmetrical bridging CF3CO2. In two formed
In complex V, the PdO2N fragments are T-shaped and point to
square-planar, but the overall geometry of the Pd centres is very
odd and difficult to classify. The PdePd bonds would complete
a typical 16-e configuration, but we have one additional ligand, the
olefin. Therefore, the electron count at each individual Pd looks like
18 electrons. The cluster has the total electron count of 66 electrons
(¼10 ꢂ 4 (Pd) þ 4 ꢂ 3 (carboxylate) þ 2 ꢂ 3 (nitrosyl) þ 4 ꢂ 2
(styrene); bridging nitrosyls are considered as 3 electron donors).
This corresponds to a 4-Pd 18-e cluster with three PdePd bonds in
total (4 ꢂ 18e3 ꢂ 2). Although there are some differences in the
PdePd bonds, they all range within 2.7084(4)e2.9894(4) Å. Thus, it
appears that they are similar in fact, and cluster V contains 6
equivalent PdePd interactions each with the 0.5-bond order.
To the best of our knowledge, V is the first example of the
tetrahedral carboxylate cluster formed by 10 groups metal.
Pd2(m-RCO2)2 subunits, the PdePd distances (2.7084(4) and 2.7594
(4) Å) are the shortest ones among the known PdePd(carboxylate)2.
In all carboxylate ligands, the differences between the PdeO(n1) and
PdeO(n2) distances (n ¼ 1e4, Table 2) are longer than 0.3 Å. Of
interest, all PdeO(n1) bonds lie opposite to the NO ligands in the
coordination spheres of Pd atoms. As a result of this distortion, the
Pd2(
m
-RCO2) fragments are not planar and the OePdePdeO torsion
Apparently, the formation of complex V includes the following
steps: the action of excess styrene molecules leads to a splitting of
trinuclear molecule IV into mononuclear fragment [(PhCH]CH2)
angles vary from 16.0(1) to 22.3(1)ꢀ. The rest two edges of the Pd4
tetrahedron (Pd(1)ePd(4) and Pd(2)ePd(3)) are not occupied by any
bridging ligands. In V, the geometrical features of
h
2-coordinated
(NO)Pd(CF3CO2)2] and binuclear fragment [(PhCH]CH2)(NO)Pd(
m-
styrene molecule are similar to those found in structure IV.
CF3CO2)Pd(PhCH¼CH2)(
m
-CF3CO2)] as the main building blocks.
Steric hindrances in binuclear fragments resulted from styrene
coordinationrequirements forcethese twofragments tobearranged
perpendicularly. Finally, the transformation of the terminal NO-
groups into the bridging ones yields complex V (see Scheme 2).
Table 3
X-ray structure determination summary.
Compound
IV
V
Formula
M
Crystal system
Space group
a/Å
C24H16F12N2O10Pd3
1039.59
Triclinic
C40H32F12N2O10Pd4
1354.28
Monoclinic
Cc
11.2255(5)
23.3335(11)
17.6671(8)
90
94.549(1)
90
4613.0(4)
4
1.639
20,772
10,560 (0.0226)
0.0281
0.0695
3. Conclusion
P-1
We have described the reactivity of the linear trimer
Pd3(NO)2(m-CF3CO2)4(h h
2-C6H5Me)2 (I) containing 2-coordinated
12.2228(16)
12.2745(16)
12.6023(17)
86.123(2)
82.101(2)
60.811(2)
1635.0(4)
2
1.755
16,992
7869 (0.0244)
0.0406
0.1043
b/Å
c/Å
toluene molecule toward unsaturated hydrocarbons. The first step
of the reaction of I with L (L ¼ neohexene, styrene) includes the
ꢀ
ꢀ
a
/
b
/
replacement of toluene to form the
p complexes of general formula
ꢀ
/
Pd3(NO)2(m-CF3CO2)4(h m -
2-L)2. The cluster Pd3(NO)2( -CF3CO2)4(h2
g
V/Å3
CH2CHPh)2 (IV) was characterized by the X-ray diffraction analysis.
It represents a trinuclear nitrosyl carboxylate complex. It was
shown that under the excess of styrene, complex IV transforms to
Z
m
/mmꢁ1
Data collected
Unique data (Rint
R1 [I > 2
Pd4(m-NO)2(m-CF3CO2)4(h
2-CH2CHPh)4 (V). According to the X-ray
)
s(I)]
data, tetrahedral palladium cluster V is the first representative of
a new type of nitrosyl carboxylate complexes.
wR2 (all data)

2088
R.E. Podobedov et al. / Journal of Organometallic Chemistry 695 (2010) 2083e2088
4. Experimental
were obtained. Element analysis: found: C 35.51, H 2.47, N 2.12%;
calc. for Pd4(NO)2(CF3CO2)4(CH2CHPh)4: C 35.50, H 2.39, N 2.07%. IR
spectrum: 1648, 1544, 1424, 1196, 1168, 1140, 940, 920, 848, 792,
4.1. General techniques and procedures
728, 705 cmꢁ1 1H NMR (CD2Cl2):
d 5.28 (dd, 1H, CH2) 5.80 (dd, 1H,
All organic solvents and liquid organic reagents were purified
and dried according to standard procedures. The unsaturated
hydrocarbon and gaseous olefins were commercially supplied.
CH2) 6.73 (dd, 1H, CH) 7.47 (m, 5H, C6H5).
Complex Pd3(NO)2(
m
-CF3CO2)4(
h
2-C6H5Me)2
I
was prepared
4.6. X-ray crystallography
according to a described procedure [7]. Microanalyses performed on
Carlo Erba Analyzer CHND-OEA 1108. IR spectra of solid samples in
a region of 400e4000 cmꢁ1 were recorded on a Zeiss SPECORD-M82
spectrophotometer. The samples of solid compounds were prepared
as suspensions in Nujol. 1H NMR spectra in CD2Cl2 were recorded on
a Bruker AVANCE 400 spectrometer with working frequencies of
400.13 (1H) and internal deuterium stabilization at room tempera-
ture. The chemical shifts of 1H nucleus are given relative to TMS.
GSeMS investigation was carried out on an Agilent Technologies
model 5973 instrument equipped with capillary column HP-1 using
helium as a carrier gas and temperature of vaporizer 250 ꢀC. Spectra
were recorded using electron impact method.
Crystal data and details of the X-ray analyses are given in Table 3.
All experimental datasets were collected on a Bruker SMART APEX
II diffractometer using graphite monochromatized MoeK
a radia-
tion (
l
¼ 0.71073 Å) at 150 K. Absorption corrections based on
measurements of equivalent reflections were applied. The struc-
tures were solved by direct methods and refined by full-matrix
least-squares on F2 with anisotropic thermal parameters for all
non-hydrogen atoms [17] (except disordered trifluoromethyl and
nitrosyl groups). In IV, three CF3 groups were found to be rota-
tionally disordered over three positions with occupancy ratios 0.35/
0.33/0.32, 0.60/0.25/0.15 and 0.52/0.28/0.20. One NO ligand is also
rotationally disordered over two positions (0.53/0.47). All hydrogen
atoms were placed in calculated positions and refined using the
riding model.
4.2. Reaction I with ethylene or propylene
0.4 g (0.04 mmol) complex I was dissolved in 20 ml CH2Cl2 at
room temperature. Solution was placed in two-neck round-bottom
100 ml flask and stirred in C2H4 or C3H6 atmosphere for 12 h. The
color changed from dark-vinous to pale-yellow and palladium black
formation was observed. Palladium black was filtered off and
organic products were identified by GSeMS.
Acknowledgment
We are grateful to the Russian Foundation for Basic Research
(the project No. 09-03-91284) and Presidium RAS program.
4.3. Synthesis Pd3(NO)2(m-CF3CO2)4(h
2-CH2CHCMe3)2 (III)
Appendix A. Supplementary material
0.2 g (0.2 mmol) of complex I, 20 ml CH2Cl2 and 0.4 ml (3.0 mmol)
of neohexene were placed in round-bottom 50 ml flask. The color
changed from dark-vinous to deep-brown. After 1 h a solution was
evaporated on oil pump up toe5 ml, 15 ml hexane was added and
green precipitate formed. The precipitate was filtered, washed with
hexane (15 ml) and dried under vacuum. The yield is 56% based on
palladium. Element analysis: found: C 23.65, H 2.12, N 2.72%; calc.
for Pd3(NO)2(CF3CO2)4(CH2CHCMe3)2: C 24.05, H 2.42, N. 2.81%. IR
spectrum: 1680, 1656, 1408, 1196, 1152, 976, 844, 792, 728 cmꢁ1 1H
Crystallographic data (excluding structure factors) for the
structures reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publi-
cation no. CCDC 772047 and 772048. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
References
NMR (CD2Cl2):
d
1.13 (s, 9H, CH3) 4.90 (dd, 2H, CH2) 5.90 (m,1H, CH).
[1] G. Allegra, G.T. Casagrande, A. Immirzi, L. Porri, G. Vitulli, J. Am. Chem. Soc. 92
(1970) 289.
4.4. Synthesis Pd3(NO)2(
m
-CF3CO2)4(
h
2-CH2CHPh)2 (IV)
[2] G. Nardin, P. Delise, G. Allegra, Gazz. Chim. Ital. 105 (1975) 1047.
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0.2 g (0.2 mmol) complex I, 20 ml CH2Cl2, 0.35 ml (3.0 mmol)
styrene were placed in a round-bottom 50 ml flask. The reaction
mixture was stirred for 1 h. The color changed from dark-vinous to
deep-brown. The resulting solution was concentrated on an oil
pump up to 10 ml. After that 5 ml of hexane was added and yellow
prism crystals were obtained. The crystals were filtered under Ar
atmosphere. The yield is 25% based on palladium. Element analysis:
found:
CO2)4(CH2CHPh)2: C 27.75, H 1.55, N 2.69%. IR spectrum: 1720,1652,
1336, 1200, 1157, 820, 808, 728 cmꢁ1
C 27.62, H 1.46, N 2.83%; calc. for Pd3(NO)2(CF3
-
.
4.5. Synthesis Pd4(m-NO)2(m-CF3CO2)4(h
2-CH2CHPh)4 (V)
After filtration of complex V, the saturated solution was placed
in the fridge cell at ꢁ4 ꢀC for two days and brown block crystals
[17] G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112.