Unsymmetrical pincer CNN palladium complex of 7-ferrocenylmethyl-3-methyl-3,7-diazabicyclo[3.3.1]nonane

Article abstract of DOI:10.1016/j.jorganchem.2017.06.009

The new unsymmetrical ferrocenyl containing bispidine derivative 7 was synthesized as a ligand precursor in five steps starting from N-Boc-4-oxopiperidine. The corresponding palladium CNN pincer complex 8 was prepared by direct cyclopalladation of the ligand 7 with Li₂PdCl₄ in MeOH. The molecular structure of the obtained palladacycle was determined by multinuclear NMR (¹H, ¹³C, ¹⁵N) and confirmed by X-ray diffraction analysis. The pincer complex 8 demonstrated high catalytic activity in some cross-coupling reactions of aryl halides with phenylboronic acid, norbornene and ethyl acrylate.

Full text of DOI:10.1016/j.jorganchem.2017.06.009

Accepted Manuscript
Unsymmetrical pincer CNN palladium complex of 7-ferrocenylmethyl-3-methyl-3,7-
diazabicyclo[3.3.1]nonane
Ludmila A. Bulygina, Nikolay D. Kagramanov, Natalya S. Khrushcheva, Konstantin A.
Lyssenko, Aleksander S. Peregudov, Viacheslav I. Sokolov
PII:
S0022-328X(17)30404-7
10.1016/j.jorganchem.2017.06.009
JOM 19996
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 5 April 2017
Revised Date: 9 June 2017
Accepted Date: 9 June 2017
Please cite this article as: L.A. Bulygina, N.D. Kagramanov, N.S. Khrushcheva, K.A. Lyssenko, A.S.
Peregudov, V.I. Sokolov, Unsymmetrical pincer CNN palladium complex of 7-ferrocenylmethyl-3-
methyl-3,7-diazabicyclo[3.3.1]nonane, Journal of Organometallic Chemistry (2017), doi: 10.1016/
j.jorganchem.2017.06.009.
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ACCEPTED MANUSCRIPT
O
N
N
Pd
N
Cl
boc
Fe

ACCEPTED MANUSCRIPT
Unsymmetrical pincer CNN palladium complex of 7-ferrocenylmethyl-3-
methyl-3,7-diazabicyclo[3.3.1]nonane
Ludmila A. Bulygina, Nikolay D. Kagramanov, Natalya S. Khrushcheva*,
Konstantin A. Lyssenko, Aleksander S. Peregudov, Viacheslav I. Sokolov
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of
Sciences, 28 Vavilov St., 119991 Moscow, Russian Federation
* Corresponding author
E-mail address: stemos@ineos.ac.ru (N.S.Khrushcheva)
Abstract
The new unsymmetrical ferrocenyl containing bispidine derivative 7 was
synthesized as a ligand precursor in five steps starting from N-Boc-4-
oxopiperidine. The corresponding palladium CNN pincer complex 8 was
prepared by direct cyclopalladation of the ligand 7 with Li2PdCl4 in MeOH. The
molecular structure of the obtained palladacycle was determined by multinuclear
NMR (1H, 13C, 15N) and confirmed by X-ray diffraction analysis. The pincer
complex 8 demonstrated high catalytic activity in some cross-coupling reactions
of aryl halides with phenylboronic acid, norbornene and ethyl acrylate.
Keywords: Ferrocene; Bispidine; Unsymmetrical CNN pincer palladium(II)
complex; Catalytic activity; С-С Cross-coupling reactions
1. Introduction

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Since the synthesis of the first cyclopalladium complex of ferrocene derivative
dimethylaminomethylferrocene [1], the chemistry of this class of compounds was
developed actively, and today the collection of known ferrocene CN palladium
complexes includes hundreds of structures. They were obtained from the
ferrocenyl aromatic N-heterocycles, or from ferrocenylalkyl derivatives, having
in α-position C = N bond (imines, oximes, etc.) in which the nitrogen atom is sp2
hybridized. Stable dimeric cyclopalladates could be isolated usually when the
substituents on the nitrogen atoms were two methyl [1, 2] or ethyl [3] groups.
The attempts to obtain cyclopalladium complexes of the ferrocenylalkylamines
with other N-substituents were reported to be unsuccessful [4] except for a few
examples, in which complexes were isolated as monomers and palladacycle was
supported by Pd coordination with second intra- or intermolecular heteroatomic
ligand [5, 6].
Cyclopalladate complexes with intramolecular coordination of Pd with two
heteroatoms, known as the pincer complexes, became the point of active studies
due to their high stability, possibility of structural modification and exhibited
catalytic activity. In the majority of known non-symmetrical ferrocene CNN
pincer complexes at least one N atom is sp2 hybridized (Fig. 1, A-D).

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Fig.1. Examples of known ferrocenyl unsymmetrical CNN pincer palladium
complexes.
As far as we know Kang et al. [5] reported the first non-symmetrical pincer
compound of this series in which both N atoms are sp3 (Fig.1, E). Thus it can be
expected that by using the ligand with an appropriate structure including the
ferrocenylmethyl group and two amino groups it is possible to obtain a stable
pincer Pd complex with two N(sp3) atoms. The structure of 3,7-
diazabicyclo[3.3.1]nonane (bispidine) (Fig.2, 1), with its chair-chair preferential
conformation, appeared to be the appropriate base.
N
N
N
H
N
H
Pd
Cl
1
2
Fig.2. 3,7-diazabicyclo[3.3.1]nonane 1 and unsymmetrical CNN pincer
palladium complex 2.

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It is known that symmetrical 3,7-dialkylbispidines as well as their synthetic
precursors 9-bispidinones when reacted with transition metal salts, in particular,
palladium and platinum, form the NN coordination complexes [7]. In the case of
two N-allyl groups, along with NN coordinated Pt compounds the cycloplatinum
complex obtained by substituting the vinyl proton of the allyl group was isolated
[7c]. Very recently we demonstrated [8], that in the course of interaction of 3-
benzyl-7-methylbispidine with palladium salts the novel and very stable
unsymmetrical CNN pincer complex was formed [Fig. 2, 2], while the NN
coordination complex was found only as minor compound. It seems that the
replacement of the benzyl group for ferrocenylmethyl one would allow to obtain
the stable cyclopalladate with two nitrogen atoms in sp3 hybridization.
Synthesis and study of the catalytic properties in the cross-coupling reactions of
unsymmetrical CNN pincer palladium complexes is the subject of many
investigations. All of them refer to those compounds in which the palladium
atom is attached to an aromatic ring [9]. Ferrocene complexes of similar structure
are represented much less [10], and their catalytic properties in the cross-
coupling reactions were studied, to our knowledge, only in respect of one of
them [11].
In this paper we report on the synthesis of the new unsymmetrical ferrocenyl
containing CNN pincer ligand based on the bispidine frame and its
corresponding palladium complex. The obtained Pd complex was examined as a
catalyst in the cross-coupling reactions of aryl halides with phenylboronic acid,
norbornene and ethyl acrylate.
2. Result and discussion
2.1. Synthesis and characterization

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The unsymmetrical CNN pincer ligand 7 was prepared in five steps as shown in
Scheme 1.
O
O
BnNH , (CHO)n, AcOH
2
NH -NH xH O
HCOONH , Pd/C 5%
4
2
2
2
65 °C, MeOH
74%
diglyme, KOH,
150 °C
65 °C, MeOH
85%
N
N
N
N
N
N
H
N
5
4
3
66%
bn
boc
bn
boc
boc
boc
9
9
5
1
1
5
4
FcCHO, STAB
LAH, THF
8
4
3
6
2
8
6
2
Li PdCl , AcONa x 3H O
2
4
2
N
THF
83%
N
3
65 C
96%
7
MeOH
67%
N
N
N
N
7
17
Pd
15
10
17
10
11
12
boc
11
12
15
Cl
14
6
7
14
8
13
Fe
13
Fe
Fe
16
16
Scheme 1. Synthesis of the ligand 7 and unsymmetrical CNN pincer palladium
complex 8.
First, according to the previously published methods [12], N-benzyl-N-Boc-
bispidinone 3 was obtained by a double Mannich reaction from N-Boc-4-
oxopiperidine, benzylamine, and paraformaldehyde (74% yield). The Huang–
Minlon variation of Wolff–Kishner reduction of the carbonyl functionality in 3
afforded a 66% yield of bispidine 4. The N-benzyl protecting group was cleaved
from N-benzyl-N-Boc-bispidine 4 using palladium on activated charcoal (5%) as
a catalyst and ammonium formate as a hydrogen source. N-Boc-bispidine 5 was
isolated in a yield of 85%. N-Boc-N-ferrocenylmethylbispidine 6 was
synthesized by the reductive amination of ferrocenecarboxaldehyde with 5 and
sodium triacetoxyborohydride in THF in a yield of 83%. All N-Boc-protected
bispidines 3-6 were easily purified by column chromatography on SiO2 or Al2O3
(for ferrocene compound 6). Finally, lithium aluminum hydride reduction of 6
generated in almost quantitative yield N-methyl-N-ferrcenylmethylbispidine 7

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(96%), that did not require any purification. Bispidine 7 was isolated as the
orange oil that is quite stable in the solid state and less stable in solution.
The direct cyclopalladation of N-methyl-N-ferrocenylmethylbispidine 7 was
carried out in a three different ways, but the only one pincer palladium complex
8 was isolated in all cases. The attempts to isolate other Pd complexes, CN
cyclopalladium or NN coordination, from the reaction mixture failed. The most
efficiently was found to proceed the reaction of 7 and Li2PdCl4 in the presence of
stoichiometric amounts of sodium acetate monohydrate in methanol at room
temperature. This reaction afforded a 67% yield of complex 8. The interaction of
7 with PdCl2(CH3CN)2 in CH2Cl2 at room temperature resulted in the isolation
of the compound 8 in a yield of 23%. Only 14% yield of the palladium complex
8 was achieved in the reaction of ligand 7 with Na2PdCl4 and sodium acetate
monohydrate in methanol at room temperature. The unsymmetrical pincer
palladium complex 8 was isolated as an orange crystalline compound, air and
moisture stable both in the solid state and in solution. It is insoluble in most of
the common solvents (benzene, toluene, ethyl acetate, ether, acetone etc.),
slightly soluble in chloroform and moderately in dichloromethane.
The structures of the two new ferrocene bispidine derivatives 6 and 7 and
complex 8 were determined using NMR (1H, 13C and 15N), IR, EI-MS
spectroscopy data and were confirmed by elemental analyses and X-ray
diffraction analysis (for complex 8). The assignment of the signals in NMR
spectra has been performed by the use of 2D COSY, HMQC, HMBC(1H,13С) и
HMBC(1H,15N) techniques. The numbering of atoms used for NMR assignment
is shown in Scheme 1.

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Thus, the IR data of compounds 6-8 demonstrated the presence of the group of
bands relating to the vibrations of ferrocene framework, the disappearance of the
-1
band 1690 cm corresponding to the carbonyl group while going from N-Boc-
N-ferrocenylmethylbispidine 6 to N-methyl-N-ferrocenylmethylbispidine 7, the
appearance of intense bands 345 and 285 cm -1 relating to the vibrations of Pd-Cl
bonds in the IR spectra of palladium complex 8.
1
The H NMR spectrum of complex 8 is consistent with ortho-metallation of
ferrocene ring. A decrease of the overall intensity of cyclopentadienyl protons in
1
the H NMR spectrum of the complex 8 corresponds to the presence of 1,2-
disubstituted ferrocene ring and confirms the occurrence of metalation. The
13
above result is in a good agreement with the elemental analysis data. In the C
NMR spectrum of complex 8 the resonance of the new quaternary aromatic
carbon (C15-Pd) appeared at 92.67 ppm, which is consistent with previously
published data for the other ferrocene cyclopalladated complexes [13]. The
resonance of another aromatic quaternary carbon (C11-C), which appeared in the
ligand 7 at 82.76 ppm, in the complex 8 obviously shifted downfield and
observed at 94.69 ppm, as it was noted for the pincer complex 2 [8]. The
1
comparison of the H NMR spectrum of the ligand 7 with that of the
corresponding complex 8 indicates the downfield shift of most alkyl protons
upon complex formation. It should be noted, that all signals in the proton
spectrum of compound 7 are quite broadened, probably due to the partial
oxidation of the ferrocenyl moiety during the registration of the NMR spectrum.
Each proton of bispidine frame as well as the protons of CH2 at the position 10
displayed separate signals in the 1H NMR spectrum of 8. The methylene protons
at the position 9 must be magnetically nonequivalent both in the complex 8 and

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in the ligand 7, owing to the nitrogen atoms in positions 3 and 7 have different
substituents (CH2Fc and CH3). A difference in the shielding of those protons in
the complex 8 (0.09 ppm) is considerably more than in the ligand 7 (0.02 ppm).
Due to the fact that the FeCp fragment is located in a plane perpendicular to the
coordination plane of the Pd atom, the CH protons at the positions 1 and 5 are
magnetically nonequivalent. The CH2 protons pairs at the positions 2, 4, 6, 8 and
10 become diastereotopic probably due to the influence of the magnetic
anisotropy of the above fragment. This influence is also evident in the fact, that
in each pair of the diastereotopic methylene protons of NCH2-groups the proton,
which is in a lower field, is noticeably broadened. The CH2 protons of benzyl
group in the position 10 formed the AB system, upfield component of which is
appreciably more broadened in comparison with the downfield one probably due
to more close proximity one of these protons to the FeCp fragment. From the
above data it follows that 8 represents a unsymmetrical pincer CNN palladium
complex wherein the palladium atom is coordinated with two nitrogen atoms.
This is confirmed by the chemical shifts of 15N nuclei obtained from spectra
15
HMBC (1H, N). In going from the ligand 7 to the complex 8 the shielding of
the both nitrogen atoms at the position 3 and at the position 7, increases (∆δ = 5.6
and 16.3 ppm correspondingly) that consistent with the literature data for the
15N chemical shifts of sp3-hybridized nitrogen atoms coordinated to a palladium
atom [14].
The molecular structure of complex 8 was confirmed by the X-ray analysis. A
single crystal of 8 was grown by slow evaporation of CH2Cl2 solution. According
to XRD complex 8 crystallizes in the racemic space group P-1 (Fig. 3). The
palladium atom is characterized by square-planar environment that is coincide

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with the mirror plane of bispidine ligand. The latter is characterized by chair-
chair conformation. The conformation of the 5-membered Pd(1), N(3), C(11),
C(15), C(10) cycle is flattened envelope with the deviation of C(10) atom by
0.103(6)Å. The cyclopentadienyl rings are in eclipsed conformation. The
coordination with palladium does not perturb C-C bonds in cyclopentadienyl ring
(bonds are 1.419(6)-1.431(6) for C5H4 vs. 1.414(6)-1.430(6) for C5H3CPd one),
while cause some elongation of Fe(1)-C(15) bond up to 2.069(4) Å in
comparison with the rest ones (2.026(4)-2.050(4) Å). All intra- and
intermolecular contacts in 8 correspond to the normal Van-der-Waals C…H,
H…Cl and C…C interactions.
Fig.3. The general view of 8 in crystal in representation of non-hydrogen atoms
by probability ellipsoids of atomic displacements (p=50%). Selected bond
lengths (Å): Pd(1)-C(15) 1.944(4), Pd(1)-N(3) 2.097(4), Pd(1)-N(7) 2.175(4),
Pd(1)-Cl(1) 2.3074(10), N(3)-C(4) 1.497(5), N(3)-C(10) 1.525(6), N(7)-C(17)

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1.471(6), N(7)-C(8) 1.491(6); bond angles (°) C(15)-Pd(1)-N(3) 84.34(16),
C(15)-Pd(1)-N(7) 171.69(16), N(3)-Pd(1)-N(7) 87.43(14), C(15)-Pd(1)-Cl(1)
90.94(13), N(3)-Pd(1)-Cl(1) 175.07(10), N(7)-Pd(1)-Cl(1) 97.31(11), C(2)-N(3)-
C(4) 109.9(3), C(2)-N(3)-C(10) 107.9(3), C(4)-N(3)-C(10) 110.2(3), C(2)-N(3)-
Pd(1) 109.0(3), C(4)-N(3)-Pd(1) 108.7(3), C(10)-N(3)-Pd(1) 111.1(3), C(17)-
N(7)-C(6) 108.6(4), C(17)-N(7)-C(8) 108.5(4), C(6)-N(7)-C(8) 111.3(4), C(17)-
N(7)-Pd(1) 113.4(3), C(6)-N(7)-Pd(1) 108.4(3), C(8)-N(7)-Pd(1) 106.7(3)
2.2. Catalytic studies
In this paper we present the study results of the catalytic activity of the new
pincer complex 8 in several cross-coupling Suzuki reactions (Table 1). All the
experiments were carried out under the conditions adopted previously in our
investigations for the other unsymmetrical pincer CNN palladium complex with
ferrocenyl ligand С (Fig.1) [11a]. This allowed us to make a correct comparison
between catalytic data for complexes 8 and C, obtained both in the previous and
in the present works.
Table 1
The results of catalytic cross-coupling Suzuki reaction a.
Entry
R
T (°С)
Product
Yieldb (%)
1
2
Me
55
55
98
89
9a
9b
MeO

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3
4
5
6
Me(C=O)
Me
55
21
21
21
99
74
77
90
9c
9a
9b
9c
MeO
Me(C=O)
a Reaction conditions: aryl bromide (1 mmol), PhB(OH)2 (1.5 mmol), K2CO3
(2.0 mmol), cat. 8 (0.5 mol %), MeOH (8 mL), H2O (4 ml), 5 h.
b Isolated yields after column chromatography.
The Suzuki cross-coupling reactions were conducted with the phenylboronic acid
and three aryl bromides in MeOH/H2O for 5 h with K2CO3 as a base. When the
reactions were carried out at 55° C all aryl bromides demonstrated equally high
yields of the products (Table 1, entries 1-3). Comparative results were shown in
the reactions of these aryl bromides in the same conditions with the complex С
[11a]. However, the complex 8 proved to be an active catalyst in the Suzuki
reaction also at ambient temperature and afforded 74-90% yields of
corresponding biphenyls (Table 1, entries 4-6) in contrast to the complex С,
which was not effective at room temperature even when the reactions were
carried for 24 h [11a]. According to the presented results the better catalytic
activity in the Suzuki reactions was demonstrated by bispidine-containing
complex 8 with Pd coordinated with two N(sp3) atoms. Less active appeared to
be bipyridine-containing complex C with Pd coordinated with two N(sp2). It was
previously shown that both Pd-N (sp2) bonds in the complex C are equally stable
[15]. But in the other ferrocenyl CNN pincer complexes with Pd coordinated to
N(amine) and N(imine) the bond Pd-N(sp2) is more resistant that the Pd-N(sp3)
one [10 a, b]. From this point of view the complex C must be more stable than 8.

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It can be assumed that the higher stability of the complex C possibly would lead
to the slower generation of the true catalytic active Pd(0) particles and to the
lower activity of the complex C as it was mentioned before concerning the other
pincer palladium complexes [9a].
In addition to the Suzuki reaction, the complex 8 showed catalytic activity in
other cross-coupling reactions (Table 2). The yields of the products were
excellent in the reactions of the Heck hydroarylation of 2-norbornene (entries 1-
2) and only moderate in the Heck reaction (entries 3-4)
Table 2
a
The results of catalytic cross-coupling Heck hydroarylation of 2-norbornene
and Heck reaction b.
R
2-Norbornene
10 a,b
11 a,b
R
Hal
Ethylacrylate
R
CH=CH-COOEt
T (°С) Product Yieldc (%)
Partner reagent
Entry
R
Hal
Cat 8
(mol%)
2-Norbornene
2-Norbornene
Ethylacrylate
Ethylacrylate
1
2
3
4
H
I
0.1
0.1
0.5
0.5
65
65
97
95
48
75
10a
10b
11a
11b
MeO
Me
I
Br
Br
140
140
MeO
a Reaction conditions: aryl iodide (1 mmol), 2-norbornene (3.4 mmol), HCO2H
(3 mmol), Et3N (3.8 mmol), DMSO (5 ml), 5 h.

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b Reaction conditions: aryl bromide (1 mmol), ethyl acrylate (1.5 mmol), K2CO3
(2 mmol), DMF (5 ml), 5 h.
c Isolated yields after column chromatography.
In all cross-coupling experiments the formation of small amounts of black
palladium nanoparticles was observed, which is typical for the processes
involving phosphine-free cyclopalladated catalytic systems [16].
3. Conclusion.
In summary, we have synthesized the new unsymmetrical ferrocenyl containing
ligand based on the bispidine frame. The corresponding palladium CNN pincer
complex 8, wherein the palladium is coordinated with two N(sp3) atoms, was
prepared by direct cyclopalladation of the ligand precursor and appeared to be
the efficient catalyst in some cross-coupling reactions of aryl halides with
phenylboronic acid, norbornene and ethyl acrylate. Catalytic activity of
palladacycle 8 in the Suzuki reactions appeared to be higher than that of the
complex C where Pd is coordinated with two N(sp2) atoms.
4. Experimental
General
The NMR experiments were carried out using a Bruker AvanceTM 600
1
13
spectrometer operating at 600.22 MHz for H and 150.93 MHz for C, Bruker
AvanceTM 500 (500.13 and 125,77 MHz), Bruker AvanceTM 400 (400.13 and
100.61 MHz). The spectrometers were equipped with inverse gradient probe-
1
head. H chemical shift data are given in units δ relative TMS calibrated with
residual protonic solvent (CHCl3 at 7.26 ppm and CD2Cl2 at 5.33 ppm ). The
multiplicity of a signal is indicated as follows:br, broad; s, singlet; d, doublet; m,

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multiplet; dd, doublet of doublets. 13С сhemical shifts are given relative TMS
calibrated to the solvent, CDCl3 at 77.26 ppm and CD2Cl2 at 54.24 ppm . 1H and
13C chemical shifts were measured and assigned by 2D experiments. 2D inverse
proton detected heteronuclear shift correlation spectra, gs-HMQC (1H-13C) and
gs-HMBC (1H-13C) were obtained using standard pulse sequence from the
Bruker library. 2D gradient selected 1H-15N HMBC experiment was recorded on
a 600 MHz Bruker spectrometer (1H: 600.22 MHz; 15N:60.83 MHz) using a 5
1
mm broadband probe with z-gradient; the spectral widths of H and 15N
dimensions were 6 and 30 kHz, respectively; 16 scans were acquired for each t1
increment with total 128 increments; 100 ms was used for the evolution time of
JNH couplings (5Hz). The data was processed with zero-filling on F1 and F2
dimension. The 15N chemical shifts have been measured relative to neat
CH3NO2.
EI mass spectra were taken on a FINNIGAN POLARIS Q spectrometer at 70 eV
and the temperature of the ion chamber 250 C. IR spectra were recorded on a FT-
IR Tensor 37 spectrometer (Bruker) in KBr pellets, thin film or nujol. The
assignment of absorption bands in the IR spectra was made according to ref.
[17]. Ferrocenecarboxaldehyde [18] and PhB(OH)2 [19] were obtained according
to the literature procedures. All other chemicals and solvents were used as
purchased. All prepared in cross-coupling reactions products had been reported
1
previously and were characterized by comparison with their reported H NMR
spectra.
3-Benzyl-7-(tert-butyloxycarbonyl)-3,7-diazabicyclo[3.3.1]nonan-9-one, 3.
To a boiling suspension of paraformaldehyde (6 g, 0.2 mol) in MeOH (80 ml)
was added dropwise a solution of N-Boc-4-oxopiperidine (10 g, 0.05 mol),

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benzylamine (5.45 ml, 0.05 mol) and acetic acid (2.86 ml, 0.05 mol) in 80 ml of
MeOH. The mixture was refluxed with stirring for 6 h, diluted with water,
extracted with CH2Cl2, washed with NaHCO3 water solution, brine, dried over
Na2SO4 and evaporated. The residue was purified by SiO2 column
chromatography with AcOEt/petroleum ether (1/4) to afford 3 (12.1 g, 74 %) as a
-1
colorless oil. IR (thin film, ν , cm ): 1733 (C=O), 1694 (OC=O), 737, 700
(C6H5). EI-MS, m/z (RI, %): 330 [M]+ (5), 273 [M-t-Bu]+ (73), 229 [M-Boc]+
(16). 1H NMR (400 MHz, CDCl3) δ 7.34-7.24 (m, 5H, Ph), 4.59 (d, J = 13.3 Hz,
1H, CH2NBoc), 4.43 (d, J = 13.3 Hz, 1H, CH2NBoc), 3.54 (d, J = 13.2 Hz, 1H,
CH2Ph), 3.48 (d, J = 13.2 Hz, 1H, CH2Ph), 3.42-3.12 (m, 4H, CH2NBoc,
CH2NBn ), 2.77 - 2.61 (m, 2H, CH2NBn), 2.44 (s, 1H, CH), 2.41 (br s, 1H, CH),
1.55 (s, 9H, CMe3). 13C NMR (101 MHz, CDCl3) δ 213.58 (C=O), 154.75 (C=O,
Boc), 137.43 (ipso-Ph), 128.75 (o-Ph), 128.32 (m-Ph), 127.24 (p-Ph), 80.04
(CMe3), 61.82 (CH2Ph), 59.03 and 58.67 (CH2NBn), 50.45 and 49.75
(CH2NBoc), 47.55 (CH), 28.58 (CMe3).
3-Benzyl-7-(tert-butyloxycarbonyl)-3,7-diazabicyclo[3.3.1]nonane, 4.
To a stirring at 70° C solution of 3 (12.1 g, 0.037 mol), hydrazine monohydrate
(9 ml, 0.184 mol) and diglyme (60 ml) was added KOH (14.5 g, 0.259 mol). The
mixture was stirred at 150° C 6 h, cooled to 80° C, diluted with water (150 ml)
and stirred for 30 min. The resulting mixture was extracted with petroleum ether
(3x150 ml). The combined organic layers were washed with water, brine, dried
over Na2SO4 and evaporated. The residue was purified by SiO2 column
chromatography with AcOEt/petroleum ether (1/9) to afford 4 (7.7 g, 66 %) as a
-1
colorless oil. IR (thin film, ν , cm ): 1689 (OC=O), 736, 699 (C6H5). EI-MS,
1
m/z (RI, %): 317 [M+H]+ (21), 259 [M-t-Bu]+ (100), 215 [M-Boc]+ (39). H

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NMR (400 MHz, CDCl3) δ 7.36-7.22 (m, 5H, Ph), 4.19 (d, J = 13.0 Hz, 1H,
CH2NBoc), 4.02 (d, J = 13.1 Hz, 1H, CH2NBoc ), 3.47 (d, J = 13.6 Hz, 1H,
CH2Ph), 3.32 (d, J = 13.6 Hz, 1H, CH2Ph ), 3.20 – 2.97 (m, 3H, CH2NBoc,
CH2NBn), 2.91 (d, J = 10.8 Hz, 1H, CH2NBn), 2.25 (d, J = 10.8 Hz, 1H,
CH2Bn), 2.18 (d, J = 10.8 Hz, 1H, CH2Bn), 1.90 (br s, 1H, CH), 1.81(br s, 1H,
CH), 1.68 and 1.62 (d, AB system, J = 12.2 Hz, 2H, CH2), 1.55 (s, 9H, CMe3).
13C NMR (101 MHz, CDCl3) δ 155.08 (C=O), 139.03 (ipso-Ph), 128.59 (o-Ph),
128.07 (m-Ph), 126.63 (p-Ph), 78.73 (CMe3), 63.51 (CH2Ph), 59.03 and 58.74
(CH2NBn), 48.42 and 47.59 (CH2NBoc), 31.18 (CH2), 29.00 (CH), 28.73
(CMe3).
3-(tert-Butyloxycarbonyl)-3,7-diazabicyclo[3.3.1]nonane, 5.
A mixture of 4 (20 g, 0.063 mol), ammonium formate (16 g, 0.254 mol) and 5%
Pd/C (contains 50% H2O, 4 g) in MeOH (350 ml) was refluxed with stirring for 1
h, cooled and filtered through celite. The solution was evaporated to the volume
of 100 ml and 10 N NaOH (100 ml) was added. The mixture was refluxed with
stirring for 1 h, extracted with CHCl3, washed with brine, dried over Na2SO4 and
evaporated. The residue was purified by SiO2 column chromatography with
CHCl3/MeOH (9/1) to afford 5 (12.2 g, 85 %) as a colorless oil. IR (thin film,ν,
-1
cm ): 1691 (OC=O). EI-MS, m/z (RI, %): 227 [M+H]+ (68), 169 [M-t-Bu]+
1
(72), 126 [M-Boc+H]+ (48). H NMR (600 MHz, CDCl3) δ 4.14 – 4.05 (m 2H,
CH2NBoc ), 3.19 – 3.02 (m, 4H, CH2NBoc, CH2NH ), 2.97 (d, J = 13.1 Hz, 2H,
CH2NH), 1.89 and 1.77 (d, AB system, J = 12.6 Hz, 2H, CH2), 1.72-1.55 (m, 3H,
2CH+NH), 1.47 (s, 9H, CMe3). 13C NMR (151 MHz, CDCl3) δ 155.43 (C=O,
Boc), 79.61 (CMe3), 51.82 (CH2NH), 49.46 and 48.42 (CH2NBoc), 31.57 (CH2),
28.51 (CMe3), 28.28 (CH).

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3-(tert-Butyloxycarbonyl)-7-ferrocenylmethyl-3,7-diazabicyclo[3.3.1]nonane 6.
To a solution of 5 (1 g, 4.4 mmol) in THF (50 ml) was added
ferrocenecarboxaldehyde (1.13 g, 5.3 mmol) and by portions sodium
triacetoxyborohydride (3.50 g, 16.5 mmol). The mixture was stirred for 2 h at
room temperature, diluted with water, basified with sodium hydroxide solution to
pH 10, extracted with ether, washed with brine, dried over Na2SO4 and
evaporated. The residue was purified by Al2O3 column chromatography with
AcOEt/petroleum ether (1/9) to afford 6 (1.57 g, 83 %) as an orange powder.
M.p. 112° С. Anal.: C, 64.95; H, 7.69; N, 6.57%. Calc. for C23H32FeN2O2: C,
65.10; H, 7.60; N, 6.60%. IR (KBr, ν , cm -1): 1690 (OC=O), 1105, 998, 819, 487
(FcH). EI-MS, m/z (RI, %): 424 [M]+ (53), 368 [M-t-Bu+H]+ (14), 324 [M-
1
Boc+H]+ (28). H NMR (500 MHz, CDCl3) δ 4.18 – 4.11 (m, 1H, CH2NBoc +
2H, C5H4), 4.11 – 4.06 (s, 5H, C5H5 + m, 2H, C5H4), 3.98 (d, J = 13.0 Hz, 1H,
CH2NBoc), 3.34 (d, J = 13.3 Hz, 1H, CH2Fc), 3.26 (d, J = 13.3 Hz, 1H, CH2Fc),
3.06 (dd, J = 13.1, 3.7 Hz, 1H, CH2NBoc), 2.99 (dd, J = 13.1, 3.8 Hz, 1H,
CH2NBoc), 2.89 (d, J = 10.7 Hz, 1H, CH2NCH2Fc), 2.81 (d, J = 10.7 Hz, 1H,
CH2NCH2Fc ), 2.22 (d, J = 11.0 Hz, 2H, CH2NCH2Fc ), 2.18 (d, J = 11.0 Hz,
2H, CH2NCH2Fc ), 1.79 (br s, 1H, CH), 1.73 (br s, 1H, CH), 1.61 (d, J = 12.2
13
Hz, 1H, CH2), 1.55 – 1.47 (m, 1H, CH2 + s, 9H, CMe3). C NMR (126 MHz,
CDCl3) δ 155.21 (C=O), 83.03 (ipso-C5H4), 78.48 (CMe3), 70.06 (C5H4), 68.42
(C5H5), 67.49 (C5H4), 58.40 (CH2Fc), 57.77 and 57.55 (CH2NCH2Fc), 48.76 and
47.69 (CH2NBoc), 31.27 (CH2), 29.12 (CH), 29.02 (CH), 28.76 (CMe3)
3--ferrocenylmethyl-7-methyl-3,7-diazabicyclo[3.3.1]nonane, 7.
To a gently boiling under Ar atmosphere suspension of lithium aluminium
hydride (0.30 g, 7.9 mmol) in THF (40 ml) was slowly added a solution of 6

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(0.80 g, 1.9 mmol) in 5 ml of THF. The mixture was refluxed with stirring for 3
h. After being cooled, the reaction was quenched successively with water (0.3
ml), 40% water solution of NaOH (0.3 ml) and water (0.9 ml), stirred for 30 min,
filtered and evaporated. The crude was dissolved in CHCl3/MeOH (9/1), passed
through thin layer of Al2O3 and evaporated to afford 7 (0.62 g, 96%) as an
orange oil. Anal.: C, 67.37; H, 7.84; Fe, 16.50; N, 8.34%. Calc. for C19H26FeN2:
C, 67.46; H, 7.75; Fe, 16.51; N, 8.28%. IR (thin film, ν , cm -1): 1105, 1002, 817,
1
484 (FcH). EI-MS, m/z (RI, %): 338 [M]+ (59). H NMR (600 MHz, CD2Cl2) δ
4.18 (br s, 2H, C5H4, H13 and 14), 4.13 (br s, 2H, C5H4, H12 and15), 4.12 (br s,
5H, C5H5), 3.39 (br s, 2H, CH2Fc), 2.80 (br d, J = 9.5 Hz, 2H CH2NCH2Fc), 2.78
(br d, J = 9.7 Hz, 2H, CH2NCH3), 2.32 (dd, J = 11.0, 3.5 Hz, 2H, CH2NCH3),
2.20 (dd, J = 10.8, 3.0 Hz, 2H, CH2NCH2Fc), 2.15 (br s, 3H, CH3), 1.85 (br s,
2H, 2CH), 1.38 and 1.40 (d, AB-system, J = 12.0 Hz, 2H, CH2). 13C NMR (151
MHz, CD2Cl2) δ 82.76 (ipso-C5H4), 70.45 (C5H4, C13 and 14), 68.43 (C5H5),
67.68 (C5H4, C12 and 15), 60.01 (CH2NCH2Fc), 58.27 (CH2Fc), 56.94
(CH2NBoc), 46.37 (CH3), 30.66 (CH2), 29.91 (CH). 15N NMR (160.80 MHz,
CD2Cl2,) δ -346.8 (N7), -337.8 (N3).
(7-methyl-3,7-diazabicyclo[3.3.1]nonan-3-
ylmethyl)ferrocenyl]-(C,N,N)-palladium chloride, 8.
Method A: To a solution of Na2PdCl4 (0.458 g, 1.56 mmol) and sodium acetate
monohydrate (0.212 g, 1.56 mmol) in MeOH (30 ml) and H2O (10 ml) was
added a solution of 7 (0.526 g, 1.56 mmol) in 10 ml of MeOH. The mixture was
stirred for 6 h at room temperature, filtered through celite and evaporated. The
crude was mixed with water and extracted with chloroform. The organic layers

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were dried over Na2SO4, filtered, evaporated and purified by SiO2 column
chromatography (CHCl3, then CHCl3/MeOH = 10:1) to afford 8 (0.112 g, 14%).
Method B: To a suspension of PdCl2(CH3CN)2 (0.157 g, 0.60 mmol) in CH2Cl2
(15 ml) was added a solution of 7 (0.205 g, 0.60 mmol) in 15 ml of CH2Cl2. The
mixture was stirred for 6 h at room temperature, evaporated and purified by SiO2
column chromatography (CHCl3, then CHCl3/MeOH = 10:1) to afford 8 (0.072
g, 23%).
Method C: A mixture of PdCl2 (0.284 g, 1.60 mmol) and lithium chloride (0.081
g, 1.90 mmol) in MeOH (15 ml) was refluxed with stirring for 3 h and cooled. To
the obtained solution was added a solution of 7 (0.539 g, 1.60 mmol) and sodium
acetate monohydrate (0.217 g, 1.60 mmol) in 5 ml of MeOH. The mixture was
stirred for 5 h at room temperature, filtered through celite and evaporated. The
crude was mixed with water and extracted with chloroform. The organic layers
were dried over Na2SO4, filtered and evaporated. The solid residue was washed
with acetone and dried to afford 8 (0.516 g, 67%) as an orange crystals.
Decomposes without melting at about 180° C. Anal.: C, 47.31; H, 5.27; N, 5.84;
Cl, 7.58%. Calc. for C19H25ClFeN2Pd: C, 47.53; H, 5.46; N, 5.83; Cl, 7.38%. IR
-1
-1
(KBr, ν , cm ): 1100, 994, 813, 480 (FcH); IR (nujol, ν , cm ): 345, 285 (Pd-
Cl). EI-MS, m/z (RI, %): 478 [M]+ (23), 338 [M-PdCl+H]+ (15). 1H NMR (500
MHz, CD2Cl2) δ 4.40 (br d, J = 12.2 Hz, 1H, CH2NCH2Fc), 4.31 (br s, 1H, C5H3,
H13), 4.22 (s, 5H, C5H5), 4.04 (br s, 1H, C5H3), 4.03 (br s, 1H, C5H3), 3.77 (d, J
= 12.0 Hz, 1H, CH2NCH2Fc), 3.67 (d, J = 12.0 Hz, 1H, CH2NCH3), 3.62 (d, J =
15.2 Hz, 1H, CH2Fc), 3.55 (br d, J = 15.0 Hz, 1H, CH2Fc), 3.46 (d, J = 12.0 Hz,
1H, CH2NCH3), 3.00 (dd, J = 12.0, 2.9 Hz, 1H, CH2NCH2Fc), 2.93 (dd, J = 12.0,
3.00 Hz, 1H, CH2NCH2Fc), 2.57 (s, 3H, CH3), 2.50 (dd, J = 12.2, 3.2 Hz, 1H,

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CH2NCH3), 2.40 (dd, J = 12.3, 3.1 Hz, 1H, CH2NCH3), 2.26 (m, 1H, CH), 2.16
(m, 1H, CH), 1.81 (dm, J = 12.9 Hz, 1H, CH2), 1.72 (d, J = 12.9 Hz, 1H, CH2).
13C NMR (126 MHz, CD2Cl2) δ 94.69 (ipso-C5H3, C-C), 92.67 (ipso-C5H3, C-
Pd), 70.39 (C5H3, C13), 69.18 (CH2Fc), 69.13 (C5H5), 65.37 (C5H3), 65.31
(CH2NCH2Fc), 64.90 (CH2NCH2Fc), 61.15 (CH2NCH3), 61.00 (CH2NCH3),
60.09 (C5H3), 52.04 (CH3), 31.40 (CH2), 30.59 (CH), 30.36 (CH). 15N NMR
(160.80 MHz, CD2Cl2,) δ -363.1 (N7), -343.4 (N3).
General procedure for the Suzuki reaction
To the solution of phenylboronic acid (1.5 mmol) in MeOH (8 ml) and H2O (4
ml) was added consistently K2CO3 (2 mmol), aryl bromide (1 mmol) and
palladium complex 8 (0.5 mol %). The mixture was stirred at ambient
temperature or heated at 55° C for 5 h. Then it was diluted with water and
extracted with CHCl3. The combined organic phase was dried over Na2SO4,
evaporated and purified by chromatography on SiO2 (petroleum ether/CHCl3).
General procedure for the Heck hydroarylation of 2-norbornene.
A mixture of aryl iodide (1 mmol), 2-norbornene (3.4 mmol), HCO2H (3 mmol),
Et3N (3.8 mmol), palladium complex 8 (0.1 mol %) and DMSO (5 ml) was
stirred at 65° C for 5 h. After the reaction mixture was cooled to ambient
temperature, it was diluted with water and extracted with petroleum ether. The
combined organic layers were dried over Na2SO4, evaporated and purified by
chromatography on SiO2 (petroleum ether).
General procedure for the Heck coupling reaction.
A mixture of aryl bromide (1 mmol), ethyl acrylate (1.5 mmol), K2CO3 (2
mmol), palladium complex 8 (0.5 mol %) and DMF (5 ml) was stirred at 140° C
for 5 h. After the reaction mixture was cooled to ambient temperature, it was

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diluted with water and extracted with AcOEt. The combined organic layers were
dried over Na2SO4, evaporated and purified by chromatography on SiO2
(petroleum ether/AcOEt).
X-ray crystallography.
X-ray diffraction data for 8 were collected on a Bruker APEX II
diffractometer (λ(MoKα) = 0.71072Å, 2θ < 56.5°, φ and ω scans with 0.5° scan
step and 10 s per frame exposure). Red crystals of C19H25ClFeN2Pd at 120(2) K
are triclinic, space group P-1, a = 8.7118(10), b = 10.6395(12),
c = 11.0454(17)Å, α =61.307(2), β = 79.606(3), γ=76.765(2)°, V = 871.24(19)
Å3, Z = 2, dcalc = 1.826 g cm-3. The indexing revealed that the structure was
twinned. Frames were integrated by a narrow-frame algorithm using SAINT
software package [20], both twin domains were included in the integration.
Semi-empirical absorption correction was applied with TWINABS [21] program
using intensity data for equivalent reflections. Intensities of 4356 independent
reflections (Rint = 0.0719) out of 7356 collected were used in structure solution
and refinement. The structure was solved by direct methods and refined by the
full-matrix least-squares technique against F2 in the anisotropic-isotropic
approximation. The positions of hydrogen atoms were calculated. Hydrogen
atoms were refined in riding model with Uiso(H) equal to 1.5 Ueq(C) and
1.2 Ueq(C) of the connected methyl and other carbon atoms. The refinement
converged to R1 = 0.0422 (calculated for 3828 observed reflections with
I>2σ(I)), wR2 = 0.0973 and GOF = 1.042. The refinement was performed with
SHELX software package [22]. Atomic coordinates, bond lengths and angles
and thermal parameters have been deposited at the Cambridge Crystallographic
Data Center, CCDC number 1538852.

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•
•
•
The ferrocene CNN pincer palladium complex with two N(sp3) atoms was synthesized
The molecular structure was confirmed by X-ray diffraction analysis in single crystal
The complex demonstrates high activity as (pre)catalyst in the Suzuki reaction