Journal of Organometallic Chemistry 696 (2011) 3727e3740

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Journal of Organometallic Chemistry

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Synthesis and structural characterization of 10 -(diphenylphosphino)ferrocene-1carboxamide, its corresponding hydrazide, some heterocycles derived from the
hydrazide and palladium(II) complexes with these functional phosphinoferrocene
ligands

e

pni

Petr St
cka*, Hana Sola
rov, Ivana Csa
rov
Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12840 Prague, Czech Republic

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 29 July 2011
Received in revised form
22 August 2011
Accepted 23 August 2011

Two polar phosphinoferrocene ligands, 10 -(diphenylphosphino)ferrocene-1-carboxamide (1) and 10 (diphenylphosphino)ferrocene-1-carbohydrazide (2), were synthesized in good yields from 10 -(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) via the reactive benzotriazole derivative, 1-[10 (diphenylphosphino)ferrocene-1-carbonyl]-1H-1,2,3-benzotriazole (3). Alternatively, the hydrazide was
prepared by the conventional reaction of methyl 10 -(diphenylphosphino)ferrocene-1-carboxylate with
hydrazine hydrate, and was further converted via standard condensation reactions to three phosphinoferrocene heterocycles, viz 2-[10 -(diphenylphosphino)ferrocen-1-yl]-1,3,4-oxadiazole (4), 1-[10 (diphenylphosphino)ferrocen-1-carbonyl]-3,5-dimethyl-1,2-pyrazole (5), and 1-[10 -(diphenylphosphino)
ferrocene-1-carboxamido]-3,5-dimethylpyrrole (6). Compounds 1 and 2 react with [PdCl2(cod)]
(cod h2:h2-cycloocta-1,5-diene) to afford the respective bis-phosphine complexes trans-[PdCl2(L-kP)2]
(7, L 1; 8, L 2). The dimeric precursor [(LNC)PdCl]2 (LNC 2-[(dimethylamino-kN)methyl]phenyl-kC1)
is cleaved with 1 to give the neutral phosphine complex [(LNC)PdCl(1-kP)] (9), which is readily transformed into a ionic bis-chelate complex [(LNC)PdCl(1-k2O,P)][SbF6] (10) upon removal of the chloride
ligand with Ag[SbF6]. Pyrazole 5 behaves similarly affording the related complexes [(LNC)PdCl(5-kP)] (12)
and [(LNC)PdCl(5-k2O,P)][SbF6] (13), in which the ferrocene ligand coordinates as a simple phosphine and
an O,P-chelate respectively, while oxadiazole 4 affords the phosphine complex [(LNC)PdCl(4-kP)] (11) and
a P,N-chelate [(LNC)PdCl(4-k2N3,P)][SbF6] (14) under similar conditions. All compounds were characterized by elemental analysis and spectroscopic methods (multinuclear NMR, IR and MS). The solid-state
structures of 1,AcOEt, 2, 7,3CH3CN, 8,2CHCl3, 9,CH2Cl2,0.375C6H14, 10, and 14 were determined
by single-crystal X-ray crystallography.
2011 Elsevier B.V. All rights reserved.

Keywords:
Ferrocene
Phosphine ligands
Amides
Heterocycles
Palladium complexes
Structure elucidation

1. Introduction
While exploring the synthetic potential [1], coordination
chemistry and catalytic properties [2,3] of N-substituted phosphinoferrocene carboxamides, we realized that the corresponding
archetypal compounds, namely the primary amide and hydrazide
derivatives, remain still unknown. Actually, such derivatives
are quite rare even among compounds derived from simple
organic phosphinocarboxylic acids. Whereas the primary phosphinocarboxylic amides are rather scarce [4], the respective

* Corresponding author. Fax: 420 221 951 253.

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pni

E-mail address: stepnic@natur.cuni.cz (P. St
cka).
0022-328X/$ e see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.08.043

phosphinocarboxylic hydrazides were prepared and studied so far

only in the form of their corresponding phosphine oxides [5].
This eventually led us to synthesize primary amide and hydrazide
derivatives of 10 -(diphenylphosphosphino)ferrocene-1-carboxylic
acid (Hdpf; Scheme 1) [6], which represents the simplest
ferrocene-based phosphinoferrocene carboxylic acid. The hydrazide
was further utilized as a starting material for the preparation of three
phosphinoferrocene heterocycles, 2-[10 -(diphenylphosphino)ferrocen-1-yl]-1,3,4-oxadiazole, 1-[10 -(diphenylphosphino)ferrocen-1carbonyl]-3,5-dimethyl-1,2-pyrazole
and
1-[10 -(diphenylphosphino)ferrocene-1-carboxamido]-3,5-dimethylpyrrole. These newly
synthesized functional phosphinoferrocene donors have been
structurally characterized by a combination of conventional spectroscopic methods and single-crystal X-ray crystallography, and
were subsequently studied as ligands in palladium(II) complexes.

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3728

PPh 2

PPh 2

Fe

Fe
O
CO2H

C
NH

1 (Y = H)

Hdpf

2 (Y = NH 2)
Scheme 1.

2. Results and discussion

2.1. Preparation and characterization of the ligands
Owing to the presence of an oxidation-sensitive diphenylphosphino group, amide 1 could not be synthesized analogously to
FcCONH2 (Fc ferrocenyl), i.e., from the corresponding acyl halides
(FcCOCl or FcCOF) and ammonia or directly by FriedeleCrafts
reaction of ferrocene with carbamoyl chloride [7], without any
additional protection/deprotection steps [8]. Using a general literature method [9], however, compound 1 was obtained (Scheme 2)
via an intermediate Hdpf benzotriazolyl derivative 3, which
smoothly reacted with aqueous ammonia to give the desired
amide. Isolation by column chromatography followed by crystallization from ethyl acetateehexane afforded the amide as a stable
stoichiometric solvate 1,AcOEt in a good yield (58% isolated yield
from Hdpf).

PPh2
Fe
O

In contrast, hydrazide 2 (Scheme 2) was prepared similarly to its

non-phosphinylated counterpart (FcCONHNH2) [10] by reacting
Hdpf methyl ester (Medpf) [6a] with hydrazine hydrate in reuxing
methanol. However, unlike the efcient synthesis of FcCONHNH2,
the starting Hdpf ester was converted to 2 only partially while the
rest remained unchanged (isolated yield of 2: 46%, 86% based on
unrecovered Medpf). Because of the relatively low yield, an alternative, more efcient procedure was sought for. Even in this case,
the benzotriazolyl derivative 3 proved to be a useful intermediate,
being readily converted to 2 upon treatment with hydrazine
hydrate in THF-ethanol (Scheme 2). Isolation as described for 1 gave
analytically pure 2 in practically quantitative yield (isolated yield:
96%).
Compounds 2 was further subjected to a series of heterocyclization reactions typical for acid hydrazides (Scheme 3) [11]. Thus, upon
heating with triethyl orthoformate, the hydrazide was smoothly
converted to 1,2,4-oxadiazole 4 while acetic acid-catalyzed condensation reactions of 2 with acetylacetone and hexane-2,5-dione
produced 1-acyl-3,5-dimethyl-1,2-pyrazole 5 and 1-carboxamido3,5-dimethylpyrrole 6, respectively. Compounds 4 and 5 were readily
isolated in pure form by column chromatography. Crude heterocycle 6
was found to be contaminated by an unknown, chemically similar
side-product (ca. 10e15 mol-%; not the starting hydrazide), which
tenaciously deed removal by either repeated chromatography or
crystallization.
Compounds 1e6 were characterized by multinuclear NMR, MS
and IR spectra. Electrospray ionization (ESI) mass spectra of 1-6
supported the formulation by showing abundant pseudomolecular
ions (typically [M H/Na]). Electron impact ionization (EI) mass
spectra recorded for compounds 1 and 2 revealed signals due to
molecular ions (M,) and fragments arising by simple fragmentation (e.g., [M e C5H4CONHY] at m/z 305, [M e HOY], at m/z 395,
and [M e Y] at m/z 412 for 2; Y H for 1 and NH2 for 2). Also seen
were fragments resulting from a more complicated fragmentation
processes, which most likely involve a transfer of oxygen atom from
the C]O group to the phosphorus atom (e.g., [C5H4PPh2FeO] at

C
NH2

PPh 2

PPh 2

NH3

HC(OEt) 3

Fe

Fe

PPh2
MeSO2Bt

Fe

Fe

PPh2
N

NHNH 2

N
CO 2H

C
3

Hdpf

CH2N2

MeCOCH 2 CH 2 COMe

MeCOCH 2 COMe

NH2NH2

PPh 2

PPh 2

Fe

PPh2
NH2NH2

Fe

Fe

Me

C
NH

C
OCH3

O
C

O
Medpf

Fe

PPh2

C
2

NHNH2

Scheme 2. Synthesis of amide 1 and hydrazide 2.

Me
5

Me
6

Me

Scheme 3. Preparation of phosphinoferrocenyl heterocycles 4e6.

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m/z 321, and [Ph2PO] at m/z 201). Similar features have been
observed in the EI MS spectra of Hdpf and Medpf [12].
1
H and 13C{1H} NMR spectra of 1-6 displayed characteristic
signals of the 10 -substituted (diphenylphosphino)ferrocenyl
moiety. The spectra of 1 and 2 further comprised signals of the NH
protons while those of 3-6 showed diagnostic resonances due to
the heterocyclic substituents (4: oxadiazole CH proton at dH 8.31,
oxadiazole CH and C at dC 151.93 and 166.53, respectively; 5: methyl
resonances at dH 2.26 and 2.57/dC 13.93 and 14.66; pyrazole CH at dH
5.98/dC 110.37, and pyrazole C-Me at dC 144.35 and 151.12; 6:
equivalent CH3 groups at dH 2.10/dC 11.56; pyrrole CH at dH 5.49/dC
103.98, and pyrrole C-Me at dC 127.75). Finally, the 31P NMR signals
of 1-6 were seen in a narrow range dP 17.9 O 16.9 ppm, which is
close to that of the parent Hdpf (dP 17.6 ppm [6a]).
The solid-state structures of 1 and 2 have been determined by
single-crystal X-ray crystallography. As indicated above, the amide
was isolated in the form of the stable solvate 1,AcOEt. It crystallizes as a racemic twin with the symmetry of the chiral space
group P21 and four molecules of the amide [13] and two heavily
disordered solvent molecules per the asymmetric unit. A view of
molecule 1 in the structure is presented in Fig. 1. Because the
structure determination is of a relatively lower precision owing to
a poor quality of the available crystals (defects, disordered solvent,
twinning), the discussion of molecular geometry (Table 1) will be
restricted only to selected relevant parameters.

3729

The geometry of the phosphinoferrocenyl moieties and the

amide groups in the four crystallographically independent molecules of 1 are quite similar and compare well with the data reported
earlier for Hdpf [6a] and FcCONH2 [14,15]. The molecules differ
mainly by mutual orientation of their cyclopentadienyl rings.
Whereas molecules 1 and 3 assume conformations near to ideal
anticlinal eclipsed, molecules 2 and 4 are synclinal eclipsed (cf.
ideal values: s 144 and 72 ). The amide oxygen is oriented toward
the phosphorus atom in all four cases. Yet, the orientations of the
PPh2 moieties differ. One of the phenyl rings is always directed
away from the ferrocene unit while the other, pointing toward the
ferrocene unit, is directed to the amide oxygen in molecules 1 and 3
in which the ferrocene substituents are more remote, or away from
it in molecules 2 and 4 having a more congested synclinal eclipsed
conformation. The amide planes in the four independent molecules
do not deviate much from the planes of their parent cyclopentadienyl rings. The respective dihedral angles are below 10 .
Quite expectedly, the molecules of amide 1 assemble via
NeH,,,O hydrogen bonds between the amide groups in the crystal
(Fig. 1). The O,,,N distances fall into an interval of 2.809(8)2.923(1) . Molecules 1 and 3 in the structure associate pair-wise
into centrosymmetric dimers as it is typical for primary amides
[16]. The dimeric units are further connected to neighboring
molecules 2 and 4 located at each side of these dimers via lateral
NeH,,,O hydrogen bonds. This results in the formation of innite
ribbons running along the crystallographic axis a. The PPh2 groups
are oriented away from the polar amide groups and thus decorate
the H-bonded ribbons at the outside, forming a hydrophobic
envelope around the polar, H-bonded chain.
Compound 2 crystallizes with the symmetry of the common
monoclinic space group P21/c and one crystallographically independent molecule. The molecular structure of 2 is presented in
Fig. 2 along with selected geometric data. Likewise 1, the individual
geometric parameters of 2 are similar to those of Hdpf and
FcCONHNH2 [15]. Atoms constituting the hydrazide moiety (C11, O,
N1 and N2) are coplanar within ca. 0.1 and the (C11,O,N1) plane is
rotated from the plane of it bonding cyclopentadienyl ring by only
1.9(2) . The cyclopentadienyl rings in 2 are tilted only negligibly
(1.7(1) ), which is reected by a small variation in the individual
FeeC distances (2.033(2)-2.052(2) ). The s angle of 84 indicates
that the ferrocene substituents assume an intermediate conformation, close to synclinal eclipsed. The phosphorus atom is closer
to oxygen than to N1 of the carbohydrazide unit.
In the solid state (Fig. 2), the molecules of 2 assemble into
twisted chains by means of NeH,,,O hydrogen bonds between the
hydrazide NH proton and C]O oxygen from a proximal molecule
related by a glide plane operation. This interaction is supported by

Table 1
Selected distances and angles for 1,AcOEt (in and deg).a
Parameter

Molecule 1

Molecule 2

Molecule 3

Molecule 4

FeeCgC
FeeCgP
tilt

1.638(4)
1.646(4)
2.9(5)
142
1.26(1)
1.34(1)
119.9(8)
7(1)

1.649(4)
1.652(4)
4.7(6)
79
1.25(1)
1.33(1)
120.9(8)
9(1)

1.652(4)
1.654(4)
2.9(6)
140
1.27(1)
1.34(1)
119.6(8)
5(1)

1.642(4)
1.645(4)
6.3(6)
81
1.25(1)
1.36(1)
120.3(8)
9(1)

s
C]O
CeNH2
OCeNH2

f
Fig. 1. (a) View of molecule 1 in the crystal structure of solvated amide 1 showing
displacement ellipsoids scaled to 30% probability. (b) Hydrogen bonding interactions in
the structure of 1. For clarity, only the amide-substituted cyclopentadienyl rings and
NH hydrogens are shown. The circled numbers are used to distinguish the four crystallographically independent molecules.

Denitions: CgC and CgP are the centroids of the amide- and PPh2-substituted
cyclopentadienyl rings, respectively; tilt dihedral angle of the cyclopentadienyl
least-squares planes; s torsion angle C(n01)eCgCeCgPeC(n06) (n indicates the
molecule); f dihedral angle subtended by the amide moiety (CON) and the plane
of its parent cyclopentadienyl ring.

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YNH
C
Ph

Ph
P
[PdCl2 (cod)] + 2L

O
Cl

Fe

Pd

- cod
Fe

Cl
O

Ph

Ph

C
HNY
7 (L = 1, Y = H)
8 (L = 2, Y = NH2)
Scheme 4. Synthesis of palladium(II) bis-phosphine complexes (cod cycloocta-1,5diene).

solvating acetonitrile. The independent molecules differ by

conformation of the ferrocene ligand (see s angles in Table 2).
Similarly to solvated complex 7, the central palladium atom in the
structure of 8,2CHCl3 lies on the inversion center, which renders
only the half of the complex molecule and one molecule of
solvating chloroform located in a general position structurally
independent.

Fig. 2. (a) View of the molecule of hydrazide 2 showing 30% probability displacement
ellipsoids. Selected distances and angles (in and deg): FeeCgC 1.6466(8), FeeCgP
1.6431(8), :CpC,CpP 1.7(1); C11eO 1.237(2), C11eN1 1.337(2), N1eN2 1.413(2), PeC6
1.817(2), PeC12 1.838(2), PeC18 1.836(2); OeC11eN1 121.4(2), C11eN1eN2 121.2(1).
(b) Hydrogen bonding interactions in the structure of 2. For clarity, only pivotal atoms
from the phenyl rings are shown. The possible NeH,,,lone pair(P) interaction is
indicated by a dotted arrow. Hydrogen bond parameters: N1eH1N,,,O,
N1,,,O 2.772(2) , angle at H1N 166 ; C2eH2,,,O, C2,,,O 3.349(2) , angle at
H2 147 ; P,,,H3N z 2.93 .

a soft C2eH2,,,O hydrogen bond and possibly also by an

N2eH3N,,,P(lone electron pair) contact.
2.2. Palladium(II) complexes with ligands 1 and 2
Compounds 1 and 2 react cleanly with [PdCl2(cod)]
(cod h2:h2-cycloocta-1,5-diene) under liberation of the coordinated diene to afford the respective neutral bis-phosphine
complexes trans-[PdCl2(L-kP)2] (7, L 1; 8, L 2; Scheme 4).
These complexes are poorly soluble in common laboratory solvents
and separate as crystalline solvates directly from the reaction
mixtures when solutions containing the reaction partners are
allowed to mix slowly by liquid-phase diffusion. The composition of
the solvates obtained may change with the crystallization conditions and, mainly, during the work-up due to partial desolvation.
Formulation of 7 and 8 was supported by elemental analysis, ESI
mass spectra and by NMR spectra (only for the relatively better
soluble 7). Both complexes were characterized by single-crystal
X-ray crystallography.
Views of the molecular structures as determined for solvated
complexes are shown in Figs. 3 and 4. Selected geometric data are
presented in Table 2. The asymmetric part of the unit cell of
7,3CH3CN, isolated directly from the reaction batch, comprises two
halves of the complex molecule whose central Pd atoms reside on
the crystallographic inversion centers, and three molecules of

Fig. 3. (a) View of the complex molecule in the crystal structure of 7,3CH3CN.
Displacement ellipsoids enclose the 30% probability level. (b) Hydrogen bonding
interactions in the structure of 7,3CH3CN. For clarity, only the pivotal atoms from the
phenyl rings, amide hydrogens and relevant solvent molecules are shown.

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Fig. 4. (a) View of the complex molecule in the crystal structure of 8,2CHCl3.
Displacement ellipsoids correspond to 30% probability. (b) Hydrogen bonding interactions in the structure of 8,2CHCl3. For clarity, only the pivotal atoms from the phenyl
rings and NH hydrogens are shown, and the solvent molecules are omitted. The
N2eH3N,,,O contact has an unfavorable geometry (angle at H3N 112 ).

3731

The coordination spheres in both independent molecules of

complex 7 and in the molecule of 8 are ideally planar due to
imposed symmetry but somewhat angularly distorted as indicated
by departures of the ClePdeP angles from 90 (Table 1). Parameters
describing the coordination geometry, namely the Pd-donor
distances and the ClePdeP angle [17], are similar to the corresponding values reported earlier for trans-[PdCl2(Hdpf-kP)2],
2CH3CO2H [18].
In the crystal, each of the structurally independent molecules of
7 associate via hydrogen bonds between one of its NH atoms and
amide oxygen from a neighboring, inversion related complex
molecule (Fig. 3 [19]). The remaining NH proton is involved in
hydrogen bonding to solvating acetonitrile [20]. This leads to
a formation of innite chains propagating via the standard cyclic
amide dimers (CONH2)2. In such an array, only two of the three
molecules of solvating acetonitrile are involved in construction of the
supramolecular structure while the third lls up structural voids.
The crystal packing of 8,2CHCl3 vaguely resembles that of free
hydrazide because the carbohydrazide moieties associate by means
of C]O,,,HeN hydrogen bonds into innite chains (Fig. 4 [21]).
These interactions are supported by intramolecular NeH,,,Cl
contacts [22]. Nonetheless, since each complex molecule bears two
carbohydrazide units, the individual chains are interlinked into
innite sheets located in the bc plane in which the PdCl2 moiety can
be formally regarded a connecting unit. The molecules of the
solvent (CHCl3) are attached to these sheets via the relatively
weaker CeH,,,N2 interactions (C,,,N 3.31(1) ).
In addition to simple Pd(II) complexes, amide 1 was studied as
a ligand for the (LNC)Pd(II) fragment (LNC 2-[(dimethylamino)
methyl]phenyl; Scheme 5). Thus, a bridge cleavage reaction of
[(LNC)PdCl]2 with the stoichiometric amount of 1 gave complex 9
featuring the amidophosphine as a P-monodentate ligand. Upon
removal of the Pd-bound halide with Ag[SbF6], the amide oxygen
took up the liberated coordination site to produce a bis-chelate 10.
Compound 9 is well soluble in common medium to high-polarity
organic solvents and has a strong tendency to incorporate reaction solvents in its structure during precipitation or crystallization.
In contrast, complex 10 readily crystallizes unsolvated and in an
analytically pure form.
Complexes 9 and 10 exhibited characteristic signals of the LNC
ligand in their 1H NMR spectra, namely doublets (4JPH) due to NMe2

N
Pd
Table 2
Selected distances and angles for 7,3CH3CN and 8,2CHCl3 (in and deg).a
Parameter

PdeCl
PdeP
ClePdeP
FeeCgC
FeeCgP
tilt

s
C]O
CeN
OCeN

7,3CH3CN

8,2CHCl3

Molecule 1

Molecule 2

2.2830(8)
2.3462(7)
86.70(3)
1.648(2)
1.645(1)
5.3(2)
95
1.235(4)
1.342(4)
122.1(3)
6.3(4)

2.2859(8)
2.3293(7)
92.93(3)
1.653(1)
1.650(1)
4.3(2)
146
1.238(4)
1.332(4)
122.2(3)
14.6(3)

Cl
2

1
2.301(2)
2.358(2)
95.07(6)
1.648(3)
1.647(3)
1.8(4)
134
1.240(8)
1.316(8)
121.9(6)
19.9(7)

a
CgC and CgP are the centroids of amide- and PPh2-substituted cyclopentadienyl
rings, respectively. s torsion angle C1eCgCeCgPeC6; f dihedral angle subtended
by the amide (CON) plane and its bonding cyclopentadienyl ring.
b
Further data: N1eN2 1.439(8) , C11eN1eN2 121.3(5) .

Ph

Ph

Ph

P
Pd
Fe

Cl
O
C
NH2

SbF6

Ph

AgSbF6
- AgCl

Pd
Fe
O

C
NH2

10

Scheme 5. Synthesis of palladium(II) complexes with amide 1 and 2-[(dimethylamino-kN)methyl]phenyl-kC [1] (LNC) supporting ligand.

3732

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and NCH2 groups and four multiplets due to protons at the palladated benzene ring. The values of 4JPH coupling constants suggested
trans-PeN relationship [23] in both cases. It is noteworthy that the
ferrocene protons were observed degenerate in the spectra of both
compounds (four signals due to AA0 BB0 and AA0 BB0 X spin systems;
A, B 1H, X 31P), suggesting that conformational exibility is
maintained even after closure of the O,P-chelate ring [24]. The 31P
NMR signals were seen shifted to lower elds as compared with the
free ligand (coordination shifts: DP 49.3 ppm for 9, and 46.8 ppm
for 10), signicantly more than for the bis-phosphine complex 7
(DP 33.7 ppm). The coordination of the amide oxygen was
inferred from IR spectra, where one of two strong amide signals
around 1600 cm1 (1644 and 1607 cm1 for 1, 1655 and 1604 for 9)
appeared shifted to lower energies in 10 (1655 and 1568 cm1).
The crystal structures of 9,0.5CH2Cl2,0.375C6H14 and 10 have
been determined by single-crystal X-ray diffraction analysis. Views
of the molecular structures are presented in Fig. 5. Selected
geometric data are given in Table 3. Compound 9 crystallizes with
two molecules of the complex, one molecule of solvating CH2Cl2
and disordered hexane with a fractional occupation in the asymmetric part of the unit cell. The independent complex molecules
differ mainly in conformation, mostly in the carbamoylferrocenyl
moiety.
The individual geometric parameters determined for 9 and 10
are rather unexceptional and do not differ much from those
reported earlier for [(LNC)PdCl(Ph2PfcCONHCH2CO2Me-kP)] [2 g]
and [(LNC)Pd(Ph2PfcCONHR-k2O,P)]X (R/X Ph/SbF6 [2m] and
CH2CO2Me/ClO4 [2 g]). The coordination environments around the
palladium atoms in 9 and 10 are markedly distorted, very likely due
to a combination of unlike Pd-donor bond distances, steric
demands of the donor moieties and the presence of a relatively
small and rigid palladacycle (N.B. The CePdeN angle is the most
acute among the interligand angles). The most severely distorted is
molecule 1 in the structure of 9, which exerts a considerable
departure from an ideal planar geometry as evidenced by the
angles
subtended
by
ligands
in
trans
positions
(Cl1ePd1eC124 156.93(9) and P1ePd1eN12 165.19(8) ) and also
by the sum of the four interligand angles (ca. 365 ). The distortion
of the coordination sphere around Pd in molecule 2 (compound 9)
is similar but less pronounced as indicated by the angles
Cl2ePd2eC224 and P2ePd2eN22 being 162.7(1) and 172.3(1) ,
respectively. Accordingly, the sum of interligand angles in molecule

Table 3
Selected distances and angles for 9,0.5CH2Cl2,0.375C6H14 and 10 (in and deg).a
Parameter

PdePb
PdeCc
PdeNd
PdeE
PePdeCb,c
PePdeEb
NePdeEb,d
NePdeCb,c,d
FeeCgC
FeeCgP
tilt

s
C]O
CeN
OCeN

9,0.5CH2Cl2,0.375C6H14

10

Molecule 1 (E Cl1)

Molecule 2 (E Cl2)

(E O)

2.2455(8)
2.004(4)
2.160(3)
2.4198(9)
93.0(1)
99.01(3)
90.16(8)
82.6(1)
1.652(2)
1.651(2)
2.6(2)
140
1.243(4)
1.337(4)
122.5(3)
8.5(4)

2.2350(9)
1.993(4)
2.150(3)
2.402(1)
94.5(1)
94.07(3)
91.7(1)
81.4(2)
1.642(2)
1.646(2)
2.3(2)
144
1.230(4)
1.345(4)
122.3(3)
2.9(4)

2.2656(6)
2.000(2)
2.141(2)
2.183(2)
92.25(6)
97.79(4)
88.78(6)
81.22(8)
1.649(1)
1.650(1)
6.0(1)
63
1.264(3)
1.329(3)
119.7(2)
24.9(2)

Denitions: CgC and CgP are the centroids of the amide- and PPh2-substituted
cyclopentadienyl rings, respectively; tilt dihedral angle of the cyclopentadienyl
least-squares planes; s torsion angle C(n01)eCgCeCgPeC(n06) (n indicates the
molecule for 9); f dihedral angle subtended by the amide moiety (CON) and the
plane of its parent cyclopentadienyl ring.
b
Pd1 and P1 for 9, molecule 1; Pd2 and P2 for 9, molecule 2; Pd and P for 10.
c
C124 for 9, molecule 1; C224 for 9, molecule 2, and C24 for 10.
d
N12 for 9, molecule 1; N22 for 9, molecule 2, and N2 for 10.

2 of 9 is ca. 362 . Tetrahedral deformation of the coordination

sphere in 9 is manifested also by a displacement of the N and C
donor atoms from the (Pd,Cl,P) plane, being 0.437(3) and 0.677(4)
for molecule 1, and 0.196 and 0.517(4) for molecule 2,
respectively (N.B. The minus sign is used to indicate that the atoms
are displaced in mutually opposite directions from the (Pd,Cl,P)
plane).
Rather surprisingly, the closure of the second chelate ring such
in the complex cation of 10 reduced angular distortion of the
coordination plane as indicated by the sum of the interligand angles
being exactly 360 , and by the trans-angles: PePdeN2
173.34(5) and OePdeC24 169.72(7) . The C and N donor atoms
in 10 deviate from the (Pd,O,P) plane by less than ca. 0.08 . On the
other hand, coordination of the amide oxygen affects the geometry
of the ferrocene ligand. The amide unit in the structure of 10 is
brought to proximity of the central Pd atom through a reorientation

Fig. 5. The molecular structures of (a) of complex 9 (molecule 1) in the structure of 9,0.5CH2Cl2,0.375C6H14, and (b) the cation in the structure of 10. Displacement ellipsoids
enclose the 30% probability level.

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of the cyclopentadienyl rings and by rotation of the amide moiety

from the plane of its parent cyclopentadienyl ring (cf. s and f angles
in Table 3). Coordination of the amide oxygen results in a slight
elongation of the C]O bond and shortening of the CeN bond
[2f,m].
The ve-membered metalacycles in the structures of 9 and 10
adopt approximate envelope conformations. Differences in
conformation of these rings, reected in the distortion of the
coordination plane, are obvious from an inspection of the respective ring puckering parameters [25,26]. The palladated benzene
rings are rotated with respect to the PdL4 plane. This rotation is
larger in 9 (36.1(2) and 32.4(2) for molecules 1 and 2, respectively) than in the more sterically more congested 10 (26.0(1) ).
In the solid state (Fig. 6), molecules of 9 assemble into innite
angular chains via NeH,,,O]C hydrogen bonds constituted by
molecules 1 or 2 along the crystallographic glide planes [27]. Polar
domains (amide moieties) of these parallel chains constituted
uniformly by molecules 1 or 2 are oriented toward each other and
are interlinked by NeH,,,O]C hydrogen bonds into innite
ribbons [28]. This ribbon-like array is further stabilized by intramolecular NeH,,,ClePd contacts, which saturate the only
remaining NH protons [29].

3733

Crystal assembly formed by ions forming the structure of 10 is

relatively simple (Fig. 6). The complex cations in the structure
associate into discrete centrosymmetric dimers via the conventional NeH,,,O hydrogen bonds [30] and these dimers further
interact via hydrogen bonds between the remaining NH protons
and uorine atoms in two adjacent (inversion related) hexauoroantimonate anions [31]. The anions are further involved in
CeH,,,F contacts with the proximal molecules.
2.3. Palladium(II) complexes with phosphinoferrocene heterocycles
4 and 5
Similarly to amide 1, the coordination properties of phosphinoferrocene heterocycles 4 and 5 were assessed in complexes of the
(LNC)Pd fragment (Scheme 6). Compound 6, which was not isolated
in pure form, was excluded from coordination study.
Heterocycles 4 and 5 readily cleaved chloride bridges in the
[(LNC)PdCl]2 dimer to afford neutral complexes 11 and 12, respectively. Upon subsequent halide removal with Ag[SbF6], the latter
complex was converted to an O,P-chelate complex 13, which is an
analog of 10. Compound 11 behaved differently, affording a P,Nchelate 14 under similar conditions. Complexes 11e14 have been
characterized by multinuclear NMR spectroscopy, ESI mass and IR
spectroscopy and by elemental analysis. The structure of 14 was
corroborated by single-crystal X-ray diffraction analysis.

N
Pd
Cl
2

L=5

L=4
Ph
Ph

Ph

Pd

P
N

Cl
N

CH3

11

12

AgSbF6

AgSbF6

- AgCl

- AgCl

SbF6

Ph

Ph

SbF6

Ph
P

Pd
Fe
N

Pd
Fe

O
Fig. 6. (a) Hydrogen bonding interactions in the structure of complex 9. Only the
pivotal atoms in the phenyl rings and amide hydrogens in for molecules 1 and only the
CeCONH2 moieties from molecules 2 are shown in order to simplify the complicated
picture. (b) Hydrogen bonding interactions in the structure of complex 10. Only the
pivotal atoms from the phenyl rings and amide hydrogens are shown for clarity.

CH3

Ph

Cl
O
C

Fe

Pd
Fe

Ph
P

14

CH3

N
CH3

13
NC

Scheme 6. Synthesis of (L )Pd complexes with 4 and 5.

3734

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1
H NMR spectra conrmed the formulation of 10e14 by
showing signals due to both the phosphinoferrocene ligands and
the LNC moiety. Notably, the spectra of chelate complexes 13 and 14
recorded at 25  C were rather broad (see Supporting Information),
which suggests a limited molecular mobility. This was conrmed by
raising the temperature of measurement to 50  C whereupon the
signals became sharper, and by cooling to 0  C, which led to
a further broadening and even to a splitting of some signals due to
locked conformations which render the ferrocene and LNC protons
diastereotopic [24]. This behavior, not observed for analogous
complex of amide 1, apparently results from steric interactions of
the bulky heterocyclic donor groups. 31P NMR signals of 10e14
were seen at positions similar to those of 9 and 10.
View of the complex cation in the structure of 14 is shown in
Fig. 7 along with selected geometric data. The observed PdeN2,
PdeP and PdeC24 distances are similar to those found for 10. The
PdeN53 distance is somewhat longer than a similar distance in
[PdCl2(LekN3)2], where L 2,5-bis(3,4,5-triethylphenyl)-1,2,4oxadiazole (2.006(2) ) [32], probably due to a relatively stronger
trans-inuence of the phosphine donor group [33] and steric
factors (chelate rings in the structure of 14). The interligand angles
within the chelating rings in 14 are more acute than the ideal 90 ,
the N2ePdeC24 angle being expectedly the most closed
(81.37(7) ). However, the closure of the in-ring angles is compensated by an opening of the remaining interligand angles and does
not therefore lead to any pronounced distortion of the coordination
environment around the palladium as indicated by the sum of the
interligand angles of 360 and by the angles subtended by donor
atoms in trans positions (N53ePdeC24 174.55(7) and
PePdeN2 176.93(5) ).
Ferrocene cyclopentadienyls in 14 assume an almost perfect
synperiplanar eclipsed conformation with s z 1. The oxadiazole
ring is rotated from the plane of its parent CpC ring by 36.8(2) ,

Fig. 7. View of the complex cation in the structure of 14 showing displacement

ellipsoids at the 30% probability level. Selected distances and angles (in and deg):
PdeP 2.2713(5), PdeN2 2.145(2), PdeN53 2.125(2), PdeC24 2.002(2), PePdeN53
88.41(4), PePdeC24 95.99(6), N2ePdeN53 94.32(6), N2ePdeC24 81.37(7); C1eC52
1.448(3), O51eC52 1.351(2), C52eN53 1.297(2), N53eN54 1.406(2), N54eC55 1.281(3),
C55eO51 1.355(3), C52eO51eC55 102.9(2), O51eC52eN53 111.1(2), C52eN53eN54
107.7(2), N53eN54eC55 104.4(2), N54eC55eO51 114.0(2).

which brings its NeN edge closer to the Pd atom. Otherwise, the
geometry of the ferrocene unit remains regular with a tilt angle of
6.3(1) and practically identical Fe-ring centroid distances (FeeCgC
1.655(1) , FeeCgP 1.653(1) ).
3. Conclusions
Polar phosphinoferrocene donors, 10 -(diphenylphosphino)
ferrocene-1-carboxamide (1) and 10 -(diphenylphosphino)ferrocene-1-carbohydrazide (2), are readily accessible from 10 -(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) in two steps. The
acid is rst converted to the reactive benzotriazole derivative 3,
which reacts smoothly with NH3 or hydrazine to afford the amide
derivatives in high yields. The hydrazide is available also by
a conventional route from 10 -(diphenylphosphino)ferrocene-1carboxylate, albeit in a considerably lower yield due to low
conversions of the starting ester. As exemplied by the synthesis of
compounds 4e6, hydrazide 2 is a convenient entry to phosphinoferrocene heterocycles, whose chemistry has been rather neglected
so far [34].
As typical hybrid ligands, compounds 1, 2, 4 and 5 coordinate to
soft Pd(II) ion preferably via their soft P-donor moiety. However,
a bidentate coordination can be readily enforced by removal of
a Pd-bound ligand (halide) to produce O,P- or N,P-chelated
complex cations depending on the type of the polar donor group
in position 10 of the ferrocene moiety (1 and 5 vs. 4). When uncoordinated, the amide and hydrazide moieties take part in hydrogen
bonding interactions, giving rise to highly variable supramolecular
arrays.
4. Experimental
4.1. Materials and methods
All syntheses were performed under an argon atmosphere and
with an exclusion of direct day light. Hdpf and Medpf [6a],
1-(methanesulfonyl)-1H-1,2,3-benzotriazole [9], [PdCl2(cod)] [35]
and [(LNC)PdCl]2 [36] were prepared according to literature procedures. Dichloromethane and chloroform were dried over anhydrous potassium carbonate and distilled. THF and (1,4-)dioxane
were dried over sodium metal and distilled under argon. Methanol,
pentane-2,4-dione and hexane-3,5-dione were freshly distilled
under argon. Anhydrous triethylamine (Fluka), acetonitrile
(Aldrich) and ethanol (Riedel-de Hen) were used as received. All
other chemicals and solvents used for crystallizations and chromatography were also used without any further purication (Fluka,
Aldrich; solvents from Lach-Ner and Penta).
NMR spectra were measured with a Varian UNITY Inova 400
spectrometer (1H, 399.95; 13C, 100.58; 31P, 161.90 MHz) at 298 K.
Chemical shifts (d/ppm) are given relative to internal tetramethylsilane (1H and 13C) or to external 85% aqueous H3PO4 (31P). The
NMR signals were assigned on the basis of a comparison with the
data reported related compounds (Hdpf and amides derived
thereof, corresponding heterocycles with organic substituents etc.).
Standard notation of the signal multiplicity is employed. In addition, vt and vq are used to denote virtual multiplets due to
magnetically non-equivalent AA0 BB0 and AA0 BB0 X spin systems of
the amide- and phosphorus-substituted cyclopentadienyl rings,
respectively (fc ferrocen-1,10 -diyl; Bt 1,2,3-benzotriazol-1-yl).
The multiplicity 13C{1H} NMR resonances are specied only for
non-singlet signals. IR spectra were recorded with an FT IR Nicolet
Magna 760 instrument in the range of 400e4000 cm1. Electrospray ionization mass spectra (ESI MS) were recorded on a Bruker
Esquire 3000 spectrometer. The samples were dissolved in
dichloromethane and diluted with methanol in a large excess. High

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resolution ESI MS measurements were performed with an LTQ

Orbitrap XL instrument (Thermo Fisher Scientic). Electronionization mass spectra (EI MS) were obtained with a GCT
Premier (Waters) spectrometer.
4.2. Preparation of 1-[10 -(diphenylphosphino)ferrocen-1-carbonyl]1H-1,2,3-benzotriazole (3)
1-(Methanesulfonyl)-1H-1,2,3-benzotriazole (0.789 g, 4.0 mmol),
Hdpf (1.66 g, 4.0 mmol) and triethylamine (0.61 g, 6.0 mmol) were
dissolved in dry THF (25 mL). The reaction mixture was heated at
gentle reux overnight and then evaporated under vacuum. The
residue was taken up with chloroform (25 mL) and the extract was
washed with water. The organic layer was dried (MgSO4) and
evaporated. The crude product was puried by ash chromatography (silica gel, dichloromethane) to afford 3 as a red solid. Yield:
1.66 g (81%).
1
H NMR (CDCl3): d 4.16 (vq, J0 1.8 Hz, 2 H), 4.42 (vt, J0 1.8 Hz,
2 H), 4.58 (vt, J0 2.0 Hz, 2 H) and 5.44 (vt, J0 2.1 Hz, 2 H) (4  CH
of fc); 7.27e7.35 (m, 10 H, PPh2), 7.49e7.54 (m, 1 H), 7.63e7.68 (m,
1 H), 8.14 (td, JHH 8.3, 1.0 Hz, 1 H) and 8.35 (td, JHH 8.3, 1.0 Hz,
1 H) (4  CH of Bt) ppm. 31P{1H} NMR (CDCl3): d 17.9 (s) ppm. 13C
{1H} NMR (CDCl3): d 71.76 (s, 1 C, Cipso fc), 73.50 (d, JPC 4 Hz, 2 C,
CH fc), 73.92 (s, 2 C, CH fc), 74.70 (s, 2 C, CH fc), 74.84 (s, 2 C, CH fc),
79.16 (d, 1JPC 10 Hz, 1 C, Cipso fc), 114.99 (s, 1 C, CH Bt), 119.97 (s, 1 C,
CH Bt), 125.95 (s, 1 C, CH Bt), 128.24 (d, 3JPC 7 Hz, 4 C, CHm PPh2),
128.71 (s, 2 C, CHp PPh2), 130.02 (s, 1 C, CH Bt), 132.12 (s, 1 C, Cipso
Bt), 133.42 (d, 2JPC 20 Hz, 4 C, CHo PPh2), 138.17 (d, 1JPC 10 Hz,
2 C, Cipso PPh2), 145.47 (s, 1 C, Cipso Bt), 169.92 (s, 1 C, C]O) ppm. IR
(Nujol): 1683 s, 1320 w, 1304 w, 1286 m, 1258 m, 1152 m, 1132 w,
1060 m, 1041 w, 1026 m, 1002 m, 950 s, 912 w, 824 s, 739 s, 694 s,
567 m, 543 m, 486 s, 447 m, 429 m cm1. EI MS: m/z (relative
abundance) 515 (4, M$), 489 (8), 488 (27), 487 (100, [MeN2],),
486 (22), 485 (14), 411 (5), 410 (17), 398 (12), 397 (47, [Ph2PfcCO]),
395 (5), 369 (7), 364 (10), 363 (40), 362 (8), 361 (6), 350 (6), 321 (13,
[FeC5H4PPh2O]), 319 (7), 306 (12), 305 (68, [FeC5H4PPh2]), 304
(13), 303 (15), 302 (5), 285 (5), 227 (12), 226 (12, [C11H7PFe]), 215
(5), 183 (15, [PPh2e2H], 171 (37), 170 (22), 154 (6), 133 (6), 128 (5),
121 (5, [C5H5Fe]), 115 (6), 56 (12). HR MS (ESI) calc. for

C29H56
23FeN3OP ([M H] ) 516.0923, found 516.0923.
4.3. Preparation of 10 -(diphenylphosphino)-1-ferrocene
carboxamide (1)
Aqueous ammonia (6 mL 25%, ca. 54 mmol) was added to
a solution of 3 (1.61 g, 3.12 mmol) dissolved in a mixture of absolute
ethanol (6 mL) and THF (12 mL). The resultant mixture was stirred
at room temperature for 3 h whereupon it turned from original red
to orange. Then, the volatiles were removed under vacuum and the
residue was dissolved in ethyl acetate. The organic extract was
washed twice with 2 M NaOH, dried (MgSO4) and evaporated. The
crude product was puried by ash chromatography (silica gel,
dichloromethaneemethanol 10:1, v/v) and subsequently crystallized by liquid-phase diffusion from ethyl acetateehexane to afford
solvate 1,AcOEt as an orange crystalline solid (1.03 g, 72%).
1
H NMR (CDCl3): d 1.25 (t, 3JHH 7.1 Hz, 1.5 H, CH3CO2CH2CH3),
2.04 (s, 1.5 H, CH3CO2CH2CH3), 4.11 (vq, J0 1.8 Hz, 2 H, fc), 4.12 (q,
3
JHH 7.1 Hz, 1 H, CH3CO2CH2CH3), 4.27 (vt, J0 2.0 Hz, 2 H), 4.46
(vt, J0 1.8 Hz, 2 H) and 4.58 (vt, J0 2.0 Hz, 2 H) (3  CH of fc); 5.47
(s, 2 H, NH2), 7.31e7.40 (m, 10 H, PPh2) ppm. 31P{1H} NMR (CDCl3):
d 16.9 (s) ppm. 13C{1H} NMR (CDCl3): d 69.95 (s, 2 C, CH fc), 71.99
(s, 2 C, CH fc), 73.05 (d, 3JPC 2 Hz, 2 C, CH fc), 74.60 (d, 2JPC 14 Hz,
2 C, CH fc), 75.23 (s, 1 C, Cipso fc), 128.35 (d, 3JPC 7 Hz, 4 C, CHm
PPh2), 128.87 (s, 2 C, CHp PPh2), 133.50 (d, 2JPC 19 Hz, 4 C, CHo
PPh2), 138.21 (d, 1JPC 7 Hz, 2 C, Cipso PPh2), 172.35 (s, 1 C, C]O)

3735

ppm. A signal due to CeP of fc is obscured by the solvent resonance

while the 13C due to solvent were not observed due to their poor
intensities. EI MS: m/z (relative abundance) 414 (28), 413 (100,
M$), 412 (10, [MeH]), 395 (17, [MeH2O]$), 386 (9,
[Ph2PfcOH]$), 322 (12), 321 (30, [C5H4PPh2FeO]), 305 (8,
[C5H4PPh2Fe]), 227 (5), 226 (14, [C11H7PFe]), 201 (4, [Ph2PO]),
183 (9, [PPh2 e 2H], 171 (23), 170 (24), 164 (18), 146 (7), 115 (7), 80
$
(10), 72 (11), 56 (14). HR MS (EI) calc. for C23H56
20FeNOP (M )

413.0632, found 413.0639. ESI MS: m/z 436 ([L Na] ), 452
([L K]). IR (Nujol): 3483 m, 3430e3250 w, 3250e3100 m,
1737 m, 1644 s, 1607 s, 1436 w, 1351 m, 1339 m, 1308 w, 1236 w,
1181 w, 1159 m, 1114 w, 1090 m, 1068 w, 1027 m, 999 w, 910 w, 890
w, 823 m, 781 m, 741 s, 695 s, 635 m, 584 w, 541 m, 515 w, 498 s,
467 w, 452 m cm1. Anal. calc. for C23H20FeNOP$AcOEt (457.3): C
65.66, H 5.29, N 3.06%; found: C 65.81, H 5.09, N 2.95%.
4.4. Preparation of 10 -(diphenylphosphino)ferrocene-1-carbo/
hydrazide (2)
4.4.1. Method A
Hydrazine hydrate (2.5 mL, 52 mmol) was added to a solution of
Medpf (412 mg, 1.0 mmol) in methanol (12 mL) and the resulting
mixture was heated at reux for 7 h. After cooling, the mixture was
diluted with water (ca. 10 mL), the volatiles (methanol) were
removed under vacuum and the aqueous residue was cooled to
4  C. The separated solid was ltered off, washed with water and
dried under vacuum. Subsequent chromatography over silica gel
with dichloromethaneemethanol (10:1, v/v) afforded two bands.
The rst, faster-eluting contained unreacted Medpf. Evaporation of
the second band afforded 2 as orange solid. Yield: 197 mg (46%, 86%
based on unrecovered Medpf).
4.4.2. Method B
Neat hydrazine hydrate (2.3 mL, 47 mmol) was introduced to
a solution of 3 (1.22 g, 2.37 mmol) in absolute ethanol (4.5 mL) and
THF (11 mL) and the mixture was stirred at room temperature for
3.5 h. The color of the mixture changed from red to orange. The
volatiles were removed under vacuum and the residue was dissolved
in ethyl acetate. The solution was washed twice with 2 M NaOH,
dried over MgSO4 and evaporated under vacuum. Subsequent ash
chromatography (silica gel, dichloromethaneemethanol 10:1, v/v)
and crystallization from ethyl acetateehexane (liquid phase diffusion) afforded analytically pure 2 as an orange crystalline solid.
Yield: 975 mg (96%).
1
H NMR (CDCl3): d 3.94 (s, 2 H, NH2), 4.10 (vq, J0 1.8 Hz, 2 H),
4.25 (vt, J0 1.8 Hz, 2 H), 4.43 (vt, J0 2.0 Hz, 2 H) and 4.57 (vt,
J0 2.0 Hz, 2 H) (4  CH of fc); 6.97 (s, 1 H, NH), 7.31e7.39 (m, 10 H,
PPh2) ppm. 31P{1H} NMR (CDCl3): d 17.2 (s) ppm. 13C{1H} NMR
(CDCl3): d 69.15 (s, 2 C, CH fc), 71.70 (s, 2 C, CH fc), 72.78 (d,
3
JPC 4 Hz, 2 C, CH fc), 74.31 (d, 2JPC 14 Hz, 2 C, CH fc), 74.72 (s, 1 C,
Cipso fc), 77.66 (d, 1JPC 7 Hz, 1 C, Cipso fc), 128.29 (d, 3JPC 7 Hz, 4 C,
CHm PPh2), 128.80 (s, 2 C, CHp PPh2), 133.46 (d, 2JPC 20 Hz, 4 C, CHo
PPh2), 138.32 (d, 1JPC 9 Hz, 2 C, Cipso PPh2), 171.18 (s, 1 C, C]O)
ppm. EI MS: m/z (relative abundance) 429 (8), 428 (27, M$), 413
(43), 412 (100, [MeNH2]), 411 (27), 395 (25, [MeNH2OH]$), 322
(14), 321 (61, [FeC5H4PPh2O]), 319 (7), 306 (7), 305 (35,
[FeC5H4PPh2]), 304 (8), 227 (9), 226 (13, [C11H7PFe]), 202 (8), 201
(51, [Ph2PO]), 183 (13, [PPh2e2H], 171 (27), 170 (20), 56 (9). HR
$
MS (EI) calc. for C23H56
21FeN2OP (M ) 428.0741, found 428.0735.

ESI MS: m/z 429 ([L H] ), 451 ([L Na]), 467 ([L K]). IR
(Nujol): 3296 s, 1622 s, 1520 m, 1316 m, 1227 w, 1263 m, 1119 w,
1031 m, 968 m, 835 m, 826 m, 744 s, 697 m, 671 w, 590 w, 569 w,
535 w, 521 w, 499 m, 446 s, 409 w cm1. Anal. calc. for C23H21FeN2OP (428.2): C 64.50, H 4.94, N 6.54%; found: C 64.43, H 4.97, N
6.49%.

3736

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4.5. Preparation of 2-[10 -(diphenylphosphino)ferrocen-1-yl]-1,3,4oxadiazole (4)

calc. for C28H25FeN2OP$0.2CH2Cl2 (509.3): C 66.50, H 5.03, N 5.50%;

found: C 66.54, H 5.01, N 5.14%.

A suspension of hydrazide 3 (107 mg, 0.25 mmol) in triethyl

orthoformate (3.5 mL, ca. 21 mmol) was sonicated for 5 min and
then heated to 140  C (temperature in bath) for 5 h during which
time the solid completely dissolved and some dark material separated. After cooling to room temperature, the mixture was evaporated under vacuum and the residue was puried by column
chromatography (silica gel, dichloromethaneemethanol, 20:1 v/v),
affording oxadiazole 4 as an orange solid after evaporation. Yield:
85 mg (78%).
1
H NMR (CDCl3): d 4.11 (vq, J0 1.8 Hz, 2 H), 4.34 (vt, J0 1.8 Hz,
2 H), 4.37 (vt, J0 1.9 Hz, 2 H) and 4.87 (vt, J0 1.9 Hz, 2 H) (4  CH of
fc); 7.31e7.37 (m, 10 H, PPh2), 8.31 (s, 1 H, CH oxadiazole) ppm. 31P
{1H} NMR (CDCl3): d 17.4 (s) ppm. 13C{1H} NMR (CDCl3): d 66.76 (s,
1 C, Cipso fc), 69.09 (s, 2 C, CH fc), 72.28 (d, 3JPC 1 Hz, 2 C, CH fc),
72.81 (d, 3JPC 4 Hz, 2 C, CH fc), 74.28 (d, 2JPC 14 Hz 2 C, CH fc),
78.64 (d, 1JPC 9 Hz, 1 C, Cipso fc), 128.27 (d, 3JPC 7 Hz, 4 C, CHm
PPh2), 128.71 (s, 2 C, CHp PPh2), 133.46 (d, 2JPC 20 Hz, 4 C, CHo
PPh2), 138.33 (d, 1JPC 10 Hz, 2 C, Cipso PPh2), 151.93 (s, 1 C, CH-5
oxadiazole), 166.53 (s, 1 C, C-2 oxadiazole) ppm. ESI MS: m/z
461 ([L Na]), 477 ([L K]). HR MS (ESI) calc. for C24H56
20FeN2OP
([M H]) 439.0657, found 439.0657. IR (Nujol): 3110 w, 3090 w,
3070 w, 1593 s, 1570 w, 1507 s, 1435 m, 1310 m, 1234 w, 1197 m, 1182
w, 1163 m, 1120 s, 1089 w, 1033 w, 1025 s, 999 w, 955 m, 918 w,
882 m, 854 w, 824 s, 750 s, 700 s, 648 s, 636 w, 569 m, 535 w, 522 w,
497 s, 453 m, 441 w cm1. Anal. calc. for C24H19FeN2OP (438.2): C
65.77, H 4.37, N 6.39%; found: C 65.84, H 4.42, N 6.13%.

4.7. Preparation of 1-[10 -(diphenylphosphino)ferrocene-1carboxamido]-3,5-dimethylpyrrole (6)

4.6. Preparation of 1-[10 -(diphenylphosphino)ferrocen-1-carbonyl]3,5-dimethyl-1,2-pyrazole (5)

Pentane-2,4-dione (1.0 mL, 10 mmol) and glacial acetic acid
(0.5 mL) were added to a solution of hydrazide 3 (428 mg,
1.0 mmol) in ethanol (10 mL) and the resulting mixture was
reuxed for 5 h. During the reuxing, the color of the mixture
turned from orange to red. After cooling, the mixture was evaporated under vacuum and the residue was taken up with dichloromethane. The solution was washed with saturated aqueous
NaHCO3, dried over MgSO4 and evaporated under vacuum. The
crude product was puried by chromatography over silica gel using
dichloromethaneemethanol (10:1 and 20:1 v/v; two runs) as the
eluent. Subsequent evaporation afforded a red oil, which slowly
solidied upon standing. Yield of 5,0.2CH2Cl2: 464 mg (91%).
1
H NMR (CDCl3): d 2.26 (s, 3 H) and 2.57 (d, J z 1.0 Hz, 3 H)
(2  CH3 pyrazole); 4.11 (vq, J0 1.8 Hz, 2 H), 4.38 (vt, J0 1.8 Hz,
2 H), 4.40 (vt, J0 2.0 Hz, 2 H) and 5.26 (vt, J0 2.0 Hz, 2 H) (4  CH
of fc); 5.29 (s, 0.4 H, CH2Cl2), 5.98 (q, J z 1 Hz, 1 H, pyrazole CH),
7.28e7.35 (m, 10 H, PPh2) ppm. 31P{1H} NMR (CDCl3): d 17.4 (s)
ppm. 13C{1H} NMR (CDCl3): d 13.93 and 14.66 (2  s, 1 C, CH3 pyrazole); 73.41 (d, JPC 4 Hz, 2 C, CH fc), 73.57 (d, JPC 2 Hz, 2 C, CH
fc), 73.78 (s, 1 C, Cipso fc), 74.29 (s, 2 C, CH fc), 74.43 (d, 2JPC 14 Hz,
2 C, CH fc), 78.18 (d, 1JPC 9 Hz, 1 C, Cipso fc), 110.37 (s, 1 C, CH
pyrazole), 128.17 (d, 3JPC 7 Hz, 4 C, CHm PPh2), 128.58 (s, 2 C, CHp
PPh2), 133.44 (d, 2JPC 20 Hz, 4 C, CHo PPh2), 138.54 (d, 1JPC 10 Hz,
2 C, Cipso PPh2), 144.35 and 151.12 (2  s, 1 C, Cipso pyrazole), 170.92
(s, 1 C, C]O). ESI MS: m/z 515 ([L Na]), 531 ([L K]). HR MS

(ESI): calc. for C28H56

25FeN2NaOP ([M Na] ) 515.0946, found
515.0945. IR (Nujol): 3120 w, 3090 w, 3080 w, 3070 w, 3050 w,
1665 s, 1585 m, 1397 w, 1346 s, 1281 m, 1222 m, 1191 m, 1162 s,
1134 m, 1096 m, 1070 w, 1039 s, 998 w, 985 w, 965 s, 951 w, 883 w,
871 w, 840 s, 822 s, 816 w, 766 s, 756 s, 742 s, 698 s, 636 m, 604 m,
581 m, 528 s, 505 s, 490 s, 460 w, 453 s, 439 w, 421 m cm1. Anal.

Hexane-2,5-dione (1.2 mL, 10 mmol) and glacial acetic acid

(0.5 mL) were added successively to a solution of hydrazide 2
(428 mg, 1.0 mmol) in absolute ethanol (10 mL) and the resulting
mixture was heated at reux for 5 h. After cooling, the mixture was
evaporated under vacuum, and the residue was partitioned
between dichloromethane and water. The organic layer was separated, washed with saturated aqueous NaHCO3, dried over MgSO4
and evaporated. The solid residue was puried by column chromatography (silica gel, dichloromethaneemethanol 10:1 and 50:1,
v/v; two runs) and then crystallized from hot ethyl acetate. The
separated solid was ltered off, washed with pentane and dried
under vacuum to give pyrrole 6 (260 mg). According to NMR
analysis, the product contained ca. 10e15 mol-% of an unknown
impurity (Ph2PfcX-type but not the starting hydrazide).
1
H NMR (CDCl3): d 2.10 (s, 6 H, CH3), 4.20 (vq, J0 1.8 Hz, 2 H),
4.35 (vt, J0 2.0 Hz, 2 H), 4.51 (vt, J0 1.8 Hz, 2 H) and 4.65 (vt,
J0 1.9 Hz, 2 H) (4  CH of fc); 5.79 (s, 2 H, pyrrole CH) 7.26e7.41 (m,
10 H, PPh2), 7.72 (br s, 1 H, NH) ppm. 31P{1H} NMR (CDCl3): d 17.2
(s) ppm. 13C{1H} NMR (CDCl3): d 11.56 (s, 2 C, CH3), 69.90 (s, 2 C, CH
fc), 72.03 (s, 2 C, CH fc), 72.92 (d, JPC 4 Hz, 2 C, CH fc), 73.88 (s, 1 C,
Cipso fc), 74.42 (d, JPC 14 Hz, 2 C, CH fc), 77.66 (d, 1JPC 7 Hz, 1 C,
Cipso fc), 103.98 (s, 2 C, CH pyrrole), 127.75 (s, 2 C, Cipso pyrrole),
128.37 (d, 3JPC 7 Hz, 4 C, CHm PPh2), 128.95 (s, 2 C, CHp PPh2),
133.44 (d, 2JPC 20 Hz, 4 C, CHo PPh2), 138.15 (d, 1JPC 9 Hz, 2 C,
Cipso PPh2), 169.18 (s, 1 C, C]O) ppm. HR MS (ESI) calc. for

C29H56
28FeN2OP ([M H] ) 507.1283 found 507.1283. ESI MS: m/z
529 ([L Na]), 545 ([L K]).
4.8. Synthesis of trans-[PdCl2(1-kP)2] (7)
A solution of [PdCl2(cod)] (14.3 mg, (0.05 mmol) in MeCN/
CH2Cl2 (1/1 v/v, 5 mL) was carefully layered with a solution of
1,AcOEt (45.7 mg, 0.10 mmol) in the same mixed solvent (5 mL).
Crystallization over several days afforded red crystals, which were
ltered off, washed with MeCN/CH2Cl2 (1/1) and dried under
vacuum. Yield: 55.7 mg (95%) of 7$MeCN$1.5CH2Cl2, red-orange
crystalline solid.
1
H NMR (DMSO): d 2.07 (s, 3 H, CH3CN), 4.47 (br vt, 4 H), 4.50 (br
vt, 4 H), 4.66 (vt, J0 z 1.9 Hz, 4 H) and 4.96 (vt, J0 z 1.9 Hz, 4 H)
(4  CH of fc); 5.75 (s, 3 H, CH2Cl2), 7.06 (s, 4 H, NH2), 7.40e7.60 (m,
20 H, PPh2) ppm. 31P{1H} NMR (CDCl3): d 16.8 (s) ppm. ESI MS:
m/z 452 ([1 K]), 967/969 ([MeCl]). IR (Nujol): 3453 w, 3405 w,
3276 w, 3158 w, 1647 s, 1609 s, 1166 m, 1103 m, 1032 m, 840 m,
745 m, 696 m, 513 m, 504 m, 472 w cm1. Anal. calc. for
C46H40Cl2Fe2N2O2P2Pd$MeCN,1.5CH2Cl2 (1172.2): C 50.72, H 3.96,
N 3.59%; found: C 50.48, H 4.00, N 3.56%.
4.9. Synthesis of trans-[PdCl2(2-kP)2] (8)
A solution of 2 (42.8 mg, 0.10 mmol) in ethanol (2 mL) was
added to a chloroform solution of [PdCl2(cod)] (14.3 mg, 0.05 mmol
in 2 mL) as a top layer. Crystallization by liquid-phase diffusion over
several days afforded red crystals, which were isolated by suction,
washed with ethanol and hexane, and dried under vacuum. Yield of
8$1.2CHCl3: 33.5 mg (57%), red crystalline solid.
ESI MS: m/z 533 ([Pd(2)]), 961 ([MeCleHCl]). IR (Nujol):
3330 w, 3310 w, 3240 w, 3204 w, 3080 w, 3050 w, 1650 s, 1626 w,
1520 s, 1436 m, 1313 s, 1228 w, 1195 w, 1164 m, 1098 s, 1061 w,
1039 s, 1027 s, 999 w, 965 m, 918 w, 876 w, 847 m, 828 m, 742 s, 710

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w, 693 s, 624 m, 593 w, 567 w, 547 m, 518 s, 503 m, 483 m, 467 m,

455 m, 438 m cm1. Anal. calc. for C46H42Cl2Fe2N4O2P2Pd$1.2CHCl3
(1177.0): C 48.16, H 3.76, N 4.76%; found: C 47.99, H 3.77, N 4.60%.
Note: The complex is insoluble in common deuterated solvents.
4.10. Synthesis of [SP-4-4]-chlorido{[(2-dimethylamino-kN)methyl]
phenyl-kC1}[10 -(diphenylphosphino-kP)-1-carbamoylferrocene]
palladium(II) (9)
[(LNC)PdCl]2 (27.6 mg, 0.05 mmol) and 1,AcOEt (45.7 mg,
0.10 mmol) were dissolved in dichloromethane (10 mL). The
resulting solution was stirred 30 min and then precipitated with
pentane. After standing at 4  C overnight, the separated solid was
ltered off, washed with pentane and dried under vacuum to give
9$CH2Cl2. Yield: 68.5 mg (94%), ne orange solid.
1
H NMR (CDCl3): d 2.86 (d, 4JPH 2.4 Hz, 6 H, NCH3), 4.13 (d,
4
JPH 1.7 Hz, 2 H, NCH2), 4.45e4.49 (m, 4 H), 4.70 (vt, J0 2.0 Hz,
2 H) and 5.04 (vt, J0 2.0 Hz, 2 H) (4  CH of fc); 5.32 (s, 1 H, CH2Cl2),
5.37 (br s, 1 H, NH2), 6.23e6.28 (m, 1 H, C6H4), 6.37 (dt, JHH 7.7,
1.6 Hz, 1 H, C6H4), 6.60 (s, 1 H, NH2), 6.81 (dt, JHH 7.3, 1.1 Hz, 1 H,
C6H4), 7.00 (dd, JHH 7.5, 1.6 Hz, 1 H, C6H4), 7.29e7.35 (m, 4 H, Ph),
7.37e7.43 (m, 2 H, Ph), 7.54e7.61(m, 4 H, Ph) ppm. 31P{1H} NMR
(CDCl3): d 32.4 (s) ppm. ESI MS: m/z 653 [MeCl]. IR (Nujol):
1655 s, 1604 s, 1164 m, 1099 m, 1028 m, 844 m, 743 s, 695 m, 505 w
cm1. Anal. calc. for C32H32ClFeN2OPPd$CH2Cl2 (731.7): C 53.34, H
4.55, N 3.83%; found C 53.42, 4.57, 3.64%.
4.11. Synthesis of [SP-4-3]-{[(2-dimethylamino-kN)methyl]phenylkC1}[10 -(diphenylphosphino-kP)-1-(carbamoyl-kO)ferrocene]
palladium(II) hexauoroantimonate (10)
Solid [(LNC)PdCl]2 (27.6 mg, 0.05 mmol) and 1,AcOEt (45.7 mg,
0.10 mmol) were dissolved in MeCN (8 mL). After stirring the
mixture for 30 min, a solution of Ag[SbF6] (34.4 mg, 0.10 mmol) in
MeCN (2 mL) was introduced causing immediate separation of an
off-white solid (AgCl). The reaction mixture was stirred for another
30 min in the dark and then ltered trough a 0.45 mm PTFE syringe
lter. The ltrate was evaporated and the crude product was
crystallized from dichloromethaneehexane by liquid phase diffusion. The separated crystals were isolated by suction, washed
successively with diethyl ether and pentane, and dried under
vacuum to afford 10 as red-orange crystalline solid. Yield: 64 mg
(72%).
1
H NMR (CD2Cl2): d 2.77 (d, 4JPH 3 Hz, 6 H, NCH3), 4.11 (vq,
J0 1.6 Hz, 2 H, fc), 4.13 (d, 4JPH 2.2 Hz, 2 H, NCH2), 4.65e4.68 (m,
4 H, fc), 5.38 (vt, J0 2.0 Hz, 2 H, fc), 6.12 (s, 1 H, NH2), 6.27 (dt,
JHH 6.6, 1.2 Hz, 1 H, C6H4), 6.35e6.41 (m, 1 H, C6H4), 6.63 (s, 1 H,
NH2), 6.86 (dt, JHH 7.3, 1.1 Hz, 1 H, C6H4), 7.00e7.03 (m, 1 H, C6H4),
7.38e7.44 (m, 4 H, Ph), 7.47e7.52 (m, 2 H, Ph), 7.70e7.76 (m, 4 H,
Ph) ppm. 31P{1H} NMR (CDCl3): d 29.9 (s) ppm. ESI MS: m/z 653
([LNCPd(1)]). IR (Nujol): 3414 m, 3338 m, 3280e3160 m, 3120 w,
3093 w, 3043 w, 1655 s, 1568 s, 1437 w, 1393 w, 1337 w, 1306 m,
1186 m, 1169 s, 1099 s, 1073 w, 1047 m, 1025 s, 997 m, 977 w, 916 w,
892 w, 856 s, 843 m, 818 s, 770 m, 750 s, 738 s, 695 s, 664 s, 643 s,
616 w, 564 m, 539 s, 522 s, 507 s, 484 m, 472 w, 457 w, 442 s cm1.
Anal. calc. for C32H32F6FeN2OPPdSb (889.6): C 43.20, H 3.63, N
3.15%; found C 43.08, H 3.62, N 3.05%.
4.12. Synthesis of [SP-4-4]-chlorido{[(2-dimethylamino-kN)methyl]
phenyl-kC1}[10 -(diphenylphosphino-kP)-1-(1,3,4-oxadiazol-2-yl)
ferrocene]palladium(II) (11)
Complex 11 was prepared similarly to 9 from [(LNC)PdCl]2
(27.6 mg, 0.05 mmol) and 4 (43.8 mg, 0.10 mmol) in 5 mL of

3737

dichloromethane. Isolation as above afforded 11 as an orange solid.

Yield: 19.6 mg (27%; the compound is highly soluble).
1
H NMR (CDCl3): d 2.89 (d, 4JPH 2.8 Hz, 6 H, NCH3), 4.16 (d,
4
JPH 2.4 Hz, 2 H, NCH2), 4.29e4.30 (m, 2 H, fc), 4.48 (vq, J0 2.0 Hz,
2 H, fc), 5.04 (vt, J0 2.0 Hz, 2 H, fc), 5.12 (vt, J0 1.9 Hz, 2 H, fc),
6.22e6.26 (m, 1 H, C6H4), 6.39 (dt, JHH 7.5, 1.2 Hz, 1 H, C6H4), 6.84
(dt, JHH 7.3, 1.1 Hz, 1 H, C6H4), 7.03 (dd, JHH 7.0, 1.5 Hz, 1 H, C6H4),
7.30e7.36 (m, 4 H, Ph), 7.38e7.45 (m, 2 H, Ph), 7.51e7.58 (m, 4 H,
Ph), 8.32 (s, 1 H, CH oxadiazole) ppm. 31P{1H} NMR (CDCl3): d 32.5
(s) ppm. ESI MS: m/z 678 [MeCl]. IR (Nujol): 1591 s, 1516 m,
1436 m, 1306 m, 1266 w, 1182 w, 1164 s, 1122 w, 1097 s, 1029 s,
993 m, 971 w, 954 m, 864 w, 844 s, 739 s, 695 s, 641 m, 629 m, 568
w, 544 s, 509 s, 478 m, 434 m cm1. Anal. calc. for C33H31ClFeN3OPPd (714.3): C 55.49, H 4.37, N 5.88%; found C 55.67, H 4.56, N
5.60%.
4.13. Synthesis of [SP-4-4]-chlorido{[(2-dimethylamino-kN)methyl]
phenyl-kC1}{1-[10 -(diphenylphosphino-kP)ferrocene-1-carbonyl]3,5-dimethyl-1,2-pyrazole}palladium(II) (12)
Pyrazole 5 (24.6 mg, 0.05 mmol) and [(LNC)PdCl]2 (13.8 mg,
0.025 mmol) were dissolved in dichloromethane (3 mL). The
mixture was stirred for 30 min and then evaporated under vacuum.
The residue was washed with pentane and dried under vacuum to
give 12 as a non-stoichiometric solvate 12,0.67C5H12. Yield:
39.8 mg (97%), an orange amorphous solid.
1
H NMR (CDCl3): d 0.85e0.91 and 1.22e1.34 (2  m, pentane);
2.18 (s, 3 H) and 2.54 (d, 4JHH z 1 Hz, 3 H) (2  CH3 pyrazole); 2.87
(d, 4JPH 2.7 Hz, 6 H, NCH3), 4.16 (d, 4JPH 2.2 Hz, 2 H, NCH2),
4.36e4.38 (m, 2 H, fc), 4.46 (vq, J0 1.9 Hz, 2 H, fc), 5.07 (vt,
J0 2.0 Hz, 2 H, fc), 5.50 (vt, J0 2.0 Hz, 2 H, fc), 5.96 (d, J z 1 Hz, 1 H,
CH pyrazole), 6.22e6.26 (m, 1 H, C6H4), 6.39 (dt, JHH 7.4, 1.2 Hz,
1 H, C6H4), 6.83 (dt, 4JHH 7.4, 1.2 Hz, 1 H, C6H4), 7.02 (dd, JHH 7.4,
1.6 Hz, 1 H, C6H4), 7.27e7.33 (m, 4 H, Ph), 7.37e7.43 (m, 2 H, Ph),
7.50e7.59 (m, 4 H, Ph) ppm. 31P{1H} NMR (CDCl3): d 32.6 (s) ppm.
ESI MS: m/z 732 [MeCl]. IR (Nujol): 3100 w, 3049 w, 1681 s,
1580 m, 1437 w, 1409 w, 1338 s, 1283 m, 1223 w, 1165 m, 1099 m,
1045 m, 993 w, 967 m, 845 s, 769 w, 745 s, 695 s, 629 m, 543 m,
505 s, 476 m, 440 w cm1. Anal. calc. for C37H37ClFeN3OPPd$0.67C5H12 (816.7): C 59.33, H 5.56, N 5.15%, found C 59.23,
H 4.52, N 4.83%.
4.14. Synthesis of [SP-4-3]-{[(2-dimethylamino-kN)methyl]phenylkC1}{1-[10 -(diphenylphosphino-kP)ferrocene-1-carbonyl]-3,5dimethyl-1,2-pyrazole-kN1}palladium(II) hexauoroantimonate (13)
A suspension of Ag[SbF6] in dichloromethane (17.2 mg,
0.05 mmol in 1 mL) was added to a solution of complex 12, which
was generated in situ by stirring a mixture of pyrazole 5 (24.6 mg,
0.05 mmol) and [(LNC)PdCl]2 (13.8 mg, 0.025 mmol) in dichloromethane (3 mL) for 30 min. After stirring for another 30 min, the
AgCl formed was ltered off and the ltrate was evaporated. The
residue was washed with pentane and dried under vacuum to
afford 13 as a red solid. Yield: 47.9 mg (quantitative).
1
H NMR (50  C, CDCl3): d 1.90 (s, 3 H) and 2.43 (d, JPH 2.4 Hz,
3 H) (2  CH3 pyrazole), 2.58 (d, 4JPH 2.8 Hz, 6 H, NCH3), 4.16 (s,
2 H, NCH2), 4.58 (s, 2 H, fc), 4.76 (s, 2 H, fc), 5.12 (s, 4 H, fc), 6.06 (s,
1 H, CH pyrazole), 6.20e6.24 (m, 1 H, C6H4), 6.34e6.38 (m, 1 H,
C6H4), 6.84 (dt, JHH 7.4, 1.1 Hz, 1 H, C6H4), 7.01 (dd, JHH 7.4, 1.6 Hz,
1 H, C6H4), 7.22e7.40 (m, 10 H, Ph) ppm. 31P{1H} NMR (CDCl3):
d 25.7 (s) ppm. ESI MS: m/z 732 [LNCPd(5)]. IR (Nujol): 3120 w,
3050 w, 1688 s, 1561 m, 1342 m, 1292 s, 1209 w, 1164 m, 1096 m,
1045 w, 997 w, 843 m, 752 s, 696 m, 659 s, 525 m, 489 m cm1. Anal.
calc. for C37H37F6FeN3OPPdSb (968.7): C 45.87, H 3.85, N 4.34%;
found C 46.13, H 4.09, N 4.06%.

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4.15. Synthesis of [SP-4-3]-{[(2-dimethylamino-kN)methyl]phenylkC1}[10 -(diphenylphosphino-kP)-1-(1,3,4-oxadiazol-2-yl-kN3)

ferrocene]palladium(II) hexauoroantimonate (14)
[(LNC)PdCl]2 (13.8 mg, 0.025 mmol) and 4 (21.9 mg, 0.05 mmol)
were reacted in dichloromethane (2 mL) for 30 min. The resulting
solution of in situ formed complex 11 was treated with a suspension
of Ag[SbF6] (17.2 mg, 0.05 mmol) in dichloromethane (ca. 1 mL). A
white precipitate (AgCl) formed immediately. After stirring for
30 min in the dark, Celite (ca. 50 mg) was added and the resulting
mixture was ltered. The ltrate was evaporated to afford
14,0.2CH2Cl2 as an orange solid. Yield: 46.2 mg (quantitative).
1
H NMR (50  C, CDCl3): d 2.66 (d, 4JPH 2.7 Hz, 6 H, NCH3), 4.07
(s, 2 H, NCH2), 4.23 (s, 2 H), 4.70 (s, 2 H), 4.82 (vt, J0 1.9 Hz, 2 H)
(3  CH of fc); 5.30 (s, 0.4 H, CH2Cl2), 5.60 (s, 2 H, CH of fc),
6.32e6.37 (m, 1 H, C6H4), 6.37e6.43 (m, 1 H, C6H4), 6.87 (dt,
JHH 7.4, 1.1 Hz, 1 H, C6H4), 7.04 (dd, JHH 7.5, 1.4 Hz, 1 H, C6H4),

7.32e7.38 (m, 4 H, Ph), 7.40e7.46 (m, 2 H, Ph), 7.64e7.72 (m, 4 H,

Ph), 8.34 (s, 1 H, CH oxadiazole) ppm. 31P{1H} NMR (CDCl3): d 28.2
(s) ppm. ESI MS: m/z 678 [LNCPd(4)]. IR (Nujol): 3150 w, 3110 w,
3050 w, 1584 s, 1530 m, 1438 w, 1313 w, 1243 w, 1166 m, 1131 w,
1098 s, 1028 m, 991 w, 970 m, 844 s, 742 s, 698 s, 659 s, 569 w, 530
w, 508 s, 482 s, 438 w cm1. Anal. calc. for C33H31F6FeN3OPPdSb$0.2CH2Cl2 (931.6): C 42.80, H 3.40, N 4.51%; found C
43.35, H 3.53, N 4.38%.
4.16. X-ray crystallography
Single-crystals suitable for X-ray diffraction analyses were obtained by recrystallization from ethyl acetateehexane (1,AcOEt
and 2), dichloromethane-hexane (9,CH2Cl2,0.375C6H14), dichloromethane-diethyl ether (10), or from chloroform-diethyl ether (14).
Crystal of bis-phosphine complexes 7 and 8 were grown by slow
diffusion of a solution of the respective ligand into a solution of

Table 4
Selected crystallographic data, data collection and structure renement parameters for 1,AcOEt, 2, 7,3CH3CN, 8,2CHCl3, 9,CH2Cl2,0.375C6H14, 10 and 14.a
Compound

1,AcOEt

7,3CH3CN

8,2CHCl3

Formula
M
Crystal system
Space group
a/
b/
c/
a/
b/
g/
V/3
Z
Dc/g mL1
m(Mo Ka)/mm1
Tb
Diffractions collected
Indep/obsdc diffrns
Rintd/%
Rd observed diffrns/%
R, wRd all data/%
Dr/e 3
CCDC reference no.

C23H20FeNOP
413.22
Monoclinic
P21e
9.9553(4)
23.487(1)
17.6041(9)

C23H21FeN2OP
428.24
Monoclinic
P21/c
7.9668(1)
26.2985(4)
9.6305(1)

C48H44Cl8Fe2N4O2P2Pd
1272.51
Monoclinic
P21/c
12.5183(6)
20.326(1)
9.6925(6)

90.254(3)

100.9761(9)

4116.2(4)
8
1.334
0.822
ef
24433
12326
7.3
6.94
11.16, 18.15
2.30, 0.66
823313

1980.82(4)
4
1.436
0.858
ef
41247
4545
4.0
2.93
3.73, 7.95
0.43, 0.40
823314

C52H49Cl2Fe2N5O2P2Pd
1126.90
Triclinic
Pe1
9.3183(2)
12.1979(2)
21.9283(5)
95.456(1)
99.957(1)
94.834(1)
2430.86(9)
2
1.540
1.177
0.819e0.958
47081
9588
4.79
3.37
5.24, 8.50
1.06, 0.99
823315

94.851(3)
2457.4(2)
2
1.720
1.490
ef
16432
3911
6.1
5.29
7.61, 15.18
1.13, 0.91
823316

Compound

9,0.5CH2Cl2,0.375C6H14

10

14

Formula
M
Crystal system
Space group
a/
b/
c/
a/
b/
g/
V/3
Z
Dc/g mL1
m(Mo Ka)/mm1
Tb
Diffractions collected
Indept/obsdc diffractions
Rdint/%
Rd observed diffrns/%
R, wRd all data/%
Dr/e 3
CCDC reference no.

C34.75H38.25Cl2FeN2OPPd
764.04
Monoclinic
P21/c
19.9670(1)
32.1880(5)
10.0820(3)

C32H32F6FeN2OPPdSb
889.57
Triclinic
Pe1
10.4844(2)
11.4409(2)
15.3705(2)
74.212(1)
78.370(1)
66.9530(9)
1623.11(5)
2
1.820
1.928
0.588e0.788
35094
7451
3.1
2.47
3.18, 5.94
1.08, 0.81
823318

C33H31F6FeN3OPPdSb
914.58
Monoclinic
P21/c
11.0877(5)
28.692(1)
10.5452(4)

90.8920(6)
6478.9(2)
8
1.567
1.249
0.581e0.916
77751
14806
6.8
4.30
6.12, 11.83
1.38, 1.57
823317

93.828(1)
3347.2(2)
4
1.815
1.874
0.593e0.816
56201
7696
1.78
1.90
2.14, 4.46
0.88, 0.39
823319

Common details: T 150(2) K.

The range of transmission factors.
c
Diffractions with I > 2s(I).
P 2
P
P
P
d
Denitions: Rint
jFo  Fo2 meanj= Fo2 , where Fo2 (mean) is the average intensity of symmetry-equivalent diffractions. R
jjFo j  jFc jj= jFo j ,
P
P
2
2 1=2
2
2
2
wR fwFo  Fc g= wFo  .
e
Flacks enantiomorph parameter 0.03(2).
f
Not corrected.
b

P.
St
epni
cka et al. / Journal of Organometallic Chemistry 696 (2011) 3727e3740

[PdCl2(cod)] (7,3MeCN: both starting materials were dissolved in

dichloromethane-acetonitrile (1/1); 8,2CHCl3: [PdCl2(cod)] was
dissolved in chloroform, the ligand in absolute ethanol).
The diffraction data (h  kl, 2q 55 ; completeness  99.6%)
were collected with a Bruker Apex2 (14) or Nonius KappaCCD (all
other) diffractometers equipped with a Cryostream cooler (Oxford
Cryosystems) using Mo Ka radiation (l 0.71073 ). Data collection, structure solution and renement parameters are summarized in Table 4.
The phase problems were solved by direct methods (SIR-97 [37]
or SHELXS-97 [38]), and the models were rened by full-matrix
least-squares based on F [2] (SHELXL-97 [38]). The non-hydrogen
atoms were rened with anisotropic displacement parameters.
NH hydrogens were identied on the difference electron density
maps and rened as riding atoms with Uiso(H) 1.2 Ueq(N). Other
hydrogen atoms were included in idealized positions and rened
similarly. The solvent molecules present in the structures of
1,AcOEt and 9,0CH2Cl2,0.375C6H14 (only hexane) were
severely disordered and their contribution to the overall scattering
was numerically subtracted using SQUEEZE [39] routine as incorporated in the PLATON program [40]. In addition, compound 1
crystallizes in the chiral space group P21 as a racemic twin. The
renement led to ca. 78:22 occupancies for the enantiomeric
components.
Geometric calculations were performed with PLATON program
and the numerical values were rounded with respect to their
estimated standard deviations given with one decimal. CCDC
deposition numbers are given in Table 4.
Acknowledgments
This work is a part of long-term research plan of the Faculty of
Science, Charles University in Prague supported by the Ministry of
Education, Youths and Sports of the Czech Republic (project nos.
MSM0021620857) and was partly supported by the Grant Agency
of Charles University in Prague (project no. 69309).
Appendix. Supplementary material
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.jorganchem.2011.08.
043.
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H1A 151 .

3740

P.
St
epni
cka et al. / Journal of Organometallic Chemistry 696 (2011) 3727e3740

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