Amidoamine-based dendrimers with end-grafted Pd-Fe units: Synthesis, characterization and their use in the Heck reaction

Article abstract of DOI:10.1016/j.jorganchem.2010.09.063

The synthesis and characterization of novel amidoamine-based metallodendrimers with heterobimetallic end-grafted amidoferrocenyl-palladium- allyl chloride units is described. Dendrimer (Fe((η⁵-C ₅H₄PPh₂)(η⁵

Full text of DOI:10.1016/j.jorganchem.2010.09.063

Journal of Organometallic Chemistry 696 (2011) 739e747
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Amidoamine-based dendrimers with end-grafted PdeFe units: Synthesis,
characterization and their use in the Heck reaction
*
Sascha Dietrich, Anja Nicolai, Heinrich Lang
Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Lehrstuhl für Anorganische Chemie, Straße der Nationen 62, 09111 Chemnitz, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 15 July 2010
Received in revised form
10 September 2010
Accepted 27 September 2010
Available online 17 November 2010
The synthesis and characterization of novel amidoamine-based metallodendrimers with heterobimetallic
end-grafted amidoferrocenyl-palladium-allyl chloride units is described. Dendrimer (Fe((
5-C5H4))C(O)HNCH2CH2NHC(O)CH2CH2)N[CH2CH2N(CH2CH2C(O)NHCH2CH2NH-C(O)(Fe(
C5H4PPh2)))2]2 (9-Fe) and the corresponding metal species (Fe((
5-C5H4PPh2(Pd( 3-C3H5)Cl))(h5
C5H4))C(O)HNCH2CH2NHC(O)CH2CH2)N[CH2CH2N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(
5-C5H4)( 5-C5H4
PPh2(Pd(
3-C3H5)Cl))))2]2 (9-FeePd) were prepared by a consecutive divergent synthesis method-
ology including additioneamidation cycles, standard peptide coupling, and coordination procedures.
For comparative reasons also the monomeric and dimeric molecules (Fe(
5-C5H4PPh2)( 5-C5H4C(O)
NHnC3H7)) (5-Fe) and [Fe( 5-C5H4PPh2)( 5-C5H4C(O)NHCH2)]2 (6-Fe) as well as N(CH2CH2C(O)
NHCH2CH2NHC(O)(Fe(
5-C5H4)( 5-C5H4PPh2)))3 (7-Fe) and [CH2N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe
5-C5H4)( 5-C5H4PPh2)))2]2 (8-Fe) were prepared from Fe( 5-C5H4PPh2)( 5-C5H4CO2H) (3). Using
[Pd(
3-C3H5)Cl]2 (4) as palladium source heterobimetallic metallodendrimers (Fe( 5-C5H4PPh2(Pd(h3
C3H5)Cl))(
5-C5H4C(O)NHnC3H7)) (5-FeePd), [Fe( 5-C5H4PPh2(Pd( 3-C3H5)Cl))( 5-C5H4C(O)NHCH2)]2 (6-
FeePd), N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(
5-C5H4)( 5-C5H4PPh2(Pd( 3-C3H5)Cl))))3 (7-FeePd) and
[CH2N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(
5-C5H4)( 5-C5H4PPh2(Pd( 3-C3H5)Cl))))2]2 (8-FeePd) were
synthesized. Additionally, seleno-phosphines of 5-FeeSe and 9-FeeSe, respectively, were prepared by
addition of elemental selenium to 5-Fe or 9-Fe to estimate their -donor properties.
h
5-C5H4PPh2)
5-C5H4)(h5
(
h
h
-
h
h
-
h
h
h
Keywords:
h
h
PAMAM-dendrimer
Ferrocenyl phosphines
Metallodendrimer
Heck-reaction
h
h
h
h
(
h
h
h
h
Cooperative effects
h
h
-
h
h
h
h
h
h
h
h
h
h
s
The palladium-containing amidoamine supports are catalytically active in the HeckeMizoroki cross-
coupling of iodobenzene with tert-butyl acrylate. The catalytic data are compared to those obtained for
the appropriate mononuclear and dinuclear compounds 5-FeePd and 6-FeePd. This comparison
confirms a positive cooperative effect. The mercury drop test showed that (nano)particles were formed
during catalysis, following on heterogeneous carbonecarbon cross-coupling.
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
amide functionalities give advantage as high capacity chelating
molecules for the stabilization of catalytic active species during the
Since the early work of G. van Koten [1] on homogeneous
catalysts immobilized on soluble inert silicon-based dendrimer
supports there is a rapid development in this field of chemistry
recognized which merges heterogeneous and homogeneous
catalysis, respectively [2]. Metallodendrimers depending on their
size properties take advantage of a simple catalyst separation and
recovery [3]. Furthermore, immobilization on a dendrimer support
may influence the activity (positive or negative dendritic effect)
and/or selectivity of a catalytic reaction, when compared with their
monomeric analogs. In addition to silicon-containing dendritic
frameworks, amidoamine dendrimers with their nitrogen and
catalytic process [4]. So far, dendrimers with peripherally attached
mononuclear organometallic or metal-organic chiral and non-
chiral units including nickel [5], palladium [6,7], platinum [8],
cobalt [9], rhodium [10,11] and ruthenium [12] fragments have
been applied in a variety of homogeneous catalyses. In this context,
the utilization of ferrocenyl phosphine functionalized supports in
combination with diverse palladium sources to in-situ generate
catalytic active species in carbonecarbon cross coupling reactions
has widely been described [13]. About the use of individual heter-
obimetallic end-grafted organometallics featuring at least one
catalytic active transition metal atom has to the best of our
knowledge not been reported in dendrimer chemistry so far,
however, very recently a method was reported to prepare the
PAMAM-based dendrimer G4OH-(Pt2þ)x(Ru3þ
)
y
by subsequent
* Corresponding author. Tel.: þ49 (0)371 531 21210; fax: þ49 (0)371 531 21219.
E-mail address: heinrich.lang@chemie.tu-chemnitz.de (H. Lang).
addition of K2[PtCl4] and [RuCl3], respectively, to dendrimer G4OH
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.09.063

740
S. Dietrich et al. / Journal of Organometallic Chemistry 696 (2011) 739e747
in an aqueous solution [14]. Nevertheless, the proposed hetero-
bimetallic PteRu complexes were not isolated.
NH2-functionalized amidoamine support (2) under standard
peptide coupling conditions in presence of HOBT
With this in mind and as a continuation of our research in the
field of dendrimers [15] and carbonecarbon cross-coupling reac-
tions [16], we here describe the immobilization of catalytic active
palladium ferrocenyl phosphines using amidoamine dendrimers.
The use of the appropriate supported heterobimetallic FeePd
systems as catalysts in the HeckeMizoroki [17e19] (reaction of
iodobenzene with tert-butyl acrylate) reaction is reported.
(¼hydroxybenzotriazole) and EDC (¼1-ethyl-3-(3-dimethylamino-
propyl)carbodiimide), respectively, which was further reacted with
[Pd(h
3-C3H5)Cl]2 (4) [21c] to give heterobimetallic 9-FeePd
(Scheme 2). Organometallic 9-FeePd was obtained in an overall
yield of 26 % (Section 4). For comparison, the organometallic
molecules 5-FeePd to 8-FeePd were synthesized in a consecutive
reaction sequence using the same reaction conditions as described
for the synthesis of 9-FeePd (Fig. 1).
2. Results and discussion
Compounds 9-Fe and 5-FeePd to 9-FeePd are odorless, stable
to air and moisture, dissolve in polar organic solvents, e.g. in
dichloromethane and tetrahydrofuran, while being poorly soluble
in benzene and toluene. Dendrimer 9-Fe featuring as terminal
group the ferrocenyl diphenylphosphine is an orange colored solid,
whereas the defined coordination compounds FeePd (5-FeePd to
9-FeePd) are bright yellow.
2.1. Synthesis of amidoamine dendrimers
Amidoamine dendrimers were prepared by a divergent consec-
utive synthesis procedure firstly described by Tomalia and
coworkers [20]. This synthesis methodology was applied to the
preparation of 2 as depicted in Scheme 1. After appropriate work-up,
this dendrimer with its five terminal amino functionalities could be
isolated as a colorless oil in almost quantitative yield (Section 4).
Dendrimer 2 was characterized by elemental analysis, IR and
NMR (1H, 13C{1H}) spectroscopy. As for related amidoamine
compounds [21a] the NMR spectroscopic characterization of 2
revealed single resonance patterns for the C(O)CH2CH2, C(O)CH2,
HNCH2, CH2NH2 and NH2 fragments of which, as expected, the
latter group appears as a broad signal (Section 4). Most character-
istic in the IR spectrum of 2 is the observation of three very
distinctive absorptions at 3365 (nNH), 1640 (nC(O), amide I), and
All ferrocenyl and heterobimetallic FeePd metallodendrimers
9-Fe and 5-FeePd to 9-FeePd gave correct elemental analyses. As
the unimolecular amidoamine molecule 2, the appropriate metal-
lodendrimer 9-FeePd shows separated and well-resolved signals
with the expected coupling pattern in the NMR spectra (Section 4).
The successful attaching of 3 to the amidoamine scaffold 2 can
nicely be proofed by IR and NMR spectroscopy. In IR spectroscopy
the absorption at ca. 1670 (nC(O)) disappears, proofing complete
consumption of the carboxylic acid (3). The formation of the amide
connectivity can best be figured with 1H NMR spectroscopy. For
example, the signal of the terminal NH2 moiety is shifted to lower
field at 7.82 ppm in course of the reaction [21a]. In the 13C{1H} NMR
spectra the resonance of the carbonyl carbon atom of the carboxylic
acid (3) is shifted from 177 to ca. 170 ppm [21b] (Section 4).
The presence of a diphenylphosphine ferrocenyl sandwich unit in
9-Fe is discernable by the appearance of a singlet at ꢀ17.9 ppm in the
31P{1H} NMR (Section 4). Through coordination of the phosphorus
atom to palladium as given in heterobimetallic compound 9-FeePd
a representative shift to lower field occurs (13.3 ppm). The chemical
1560 cmꢀ1
(nC(O), amide II) (Section 4).
2.2. Synthesis of metallo and seleniumephosphine amidoamine
dendrimers
The ironepalladium organometallic moieties were attached to
the dendrimer periphery via peptide coupling by treatment of
(diphenylphosphino)ferrocenyl carboxylic acid (3) [21b] with the
MeO
N
O
MeO
O
OMe
O
H
N
(i)
NH2
N
N
H2N
O
O
MeO
OMe
1
NH2
O
H2N
NH2
HN
N
NH
HN
O
O
(ii)
N
N
O
O
HN
NH
NH2
H2N
2
((i) CH2CHCO2Me, methanol, 25 °C, 72 hrs; (ii) H2NCH2CH2NH2, methanol, 25 °C, 72 hrs).
Scheme 1. Synthesis of amidoamine dendrimer 2.

S. Dietrich et al. / Journal of Organometallic Chemistry 696 (2011) 739e747
741
PPh2
Ph2P
Fe
Fe
HN
O
O
HN
O
HN
N
O
N
H
O
H
N
O
CO2H
(i)
N
H
N
O
Fe
N
Fe
Ph2P
PPh2
HN
NH
O
3
NH
NH
O
Fe
Ph2P
O
Fe
PPh2
9-Fe
Cl
Pd
Cl
Pd
PPh2
Ph2P
Fe
Fe
HN
HN
O
O
HN
O
O
N
H
O
H
O
N
N
H
N
(ii)
N
O
N
Fe
PPh2
HN
NH
O
Pd
Cl
Cl
NH
Pd
NH
O
Fe
Ph2P
O
Fe
PPh2
Pd
Cl
9-Fe-Pd
((i) 2, HOBT (= hydroxybenzotriazole), EDC (= 1-ethyl-3-(3-dimethylaminopropyl)-
carbodiimide, dichloromethane,
0 →
25 °C, 12 hrs; (ii) [Pd(η3-C3H5)Cl]2 (4),
dichloromethane, 25 °C, 1 h).
Scheme 2. Synthesis of heterobimetallic 9-FeePd.
shift of the datively bonded Ph2P group is, as expected, almost
independent of the appropriate amidoamine scaffold [22]. The
within the allyl unit, while in 13C{1H} spectroscopy two signals can
be assigned at ca. 62 (CH2) and 118 ppm (CH) (Section 4) [23].
newly introduced [Pd(
h
3-C3H5)Cl] organometallic fragment in 5-
The
s
-donor properties of phosphines can be quantified by
of the
FeePd to 9-FeePd can also be recognized in the 1H and 13C{1H} NMR
spectra. In the 1H NMR spectra the allyl moieties give rise to three
distinctive resonances at ca. 2.8 (CH-anti), 3.8 (CH-syn), and 5.5 ppm
(CH-centered) as a result of the different chemical environment
the phosphoruseselenium coupling constant 1J(
31Pe77Se)
appropriate seleno derivatives [24]. Therefore, we reacted the
phosphino ferrocenyl amidoamines 9-Fe and 5-Fe with selenium in
dichloromethane at ambient temperature to obtain the appropriate

742
S. Dietrich et al. / Journal of Organometallic Chemistry 696 (2011) 739e747
HN
H
N
HN
O
Fe
PPh2
Fe
O
O
Fe
Ph2P
Cl
Pd
Ph2P
Cl
Cl
Pd
Pd
5-Fe-Pd
6-Fe-Pd
Cl
Pd
O
PPh2
Fe
PPh2
Fe
O
Cl
HN
Pd
Pd
Cl
NH
Pd
Cl
O
O
NH
Ph2P
Fe
HN
H
Ph2P
N
HN
Fe
O
NH
N
O
N
O
NH
O
HN
O
O
O
N
O
Fe
N
H
HN
PPh2
Pd
HN
O
Cl
NH
Pd
Cl
NH
O
Ph2P
Fe
Fe
PPh2
Pd
Cl
7-Fe-Pd
8-Fe-Pd
Fig. 1. Heterobimetallic amidoamines 5-FeePd to 8-FeePd.
seleno-phosphine derivatives 9-FeeSe and 5-FeeSe (Fig. 2) to
classify the electronic properties of the immobilized phosphino
ferrocenes and range them with conventionally phosphines. After
appropriate work-up, 5-FeeSe and 9-FeeSe were isolated as
orange solids in almost quantitative yield (Section 4).
homogeneous palladium-catalyzed vinylation was performed as
described by Boys and Butler [27]. Thus, the appropriate organic
coupling reagents (3.0 mmol iodobenzene (10), 3.1 mmol tert-butyl
acrylate (11)) were reacted in a toluene-acetonitrile mixture of ratio
1:1 (v/v), in the presence of NEtiPr2 (3.1 mmol) as a base, [CuI] (two
equivalents) as reducing reagent [27], and a (pre)catalyst loading of
0.5 mol% of palladium at a comparative mild reaction temperature
(80 ꢁC) (Reaction 1, Fig. 3, Table 1, Section 4). The initial reaction
rate, conversion, TON (¼turn-over-number), and TOF (¼turn-over-
frequency) data are reported.
The phosphoruseselenium coupling constants of 5-FeeSe and
9-FeeSe were determined to 1J(
¼ 720 Hz (5-FeeSe) and
31Pe77Se)
723 Hz (9-FeeSe), being slightly decreased, when compared with
FcPh2P ¼ Se 1J(
¼ 731 Hz) and Ph3P ¼ Se (1J(31Pe77
¼
31Pe77Se)
Se)
729 Hz) [25]. Obviously, the immobilization on the scaffold has no
negative impact on the
s
-donor properties of the phosphines.
From Fig. 3 and Table 1 it can be seen that the best productivity
is reached with catalyst 9-FeePd possessing the highest number of
terminal heterobimetallic FeePd-units. It can also be recognized
that there is a positive synergistic effect most pronounced between
5-FeePd/6-FeePd, 7-FeePd/8-FeePd, and 9-FeePd (Fig. 3). As the
Furthermore, the phosphoruseselenium coupling constants indicate
no influence according to the number of the immobilized diphenyl-
phosphino ferrocenyl fragments.
electronic properties of all the compounds are similar (1J(
,
31Pe77Se)
2.3. Catalysis with heterobimetallic ironepalladium amidoamine
vide supra), the different catalytic activity is most likely caused by
cooperative effects between the catalytic active palladium species
formed and the amino groups of the amidoamine scaffold. The
higher the number of terminal metal fragments and of intrinsic
amino units, the higher is the catalytic activity for the embedded
palladium catalyst. Similar results of a positive “dendritic effect” on
chemical yields, which means that the activity is improved by
increasing the number of terminal metal-containing groups, have
been reported recently [3c,16e,28,29]. For all heterobimetallic
FeePd systems concomitant precipitation of metallic palladium
occurs during the catalytic reaction, which decreases in the series
5-FeePd/6-FeePd > 7-FeePd/8-FeePd > 9-FeePd.
dendrimers
To enrich the family of existing Heck catalysts, we applied the
above described heterobimetallic FeePd phosphines 5-FeePd to
9-FeePd in vinylation reactions, as metal-containing phosphines
and particularly those based on a ferrocene scaffold have played
a very important role in many organic transformations catalyzed by
palladium complexes [26]. In comparative studies these newly
synthesized compounds showed to be efficient catalysts in the
carbonecarbon cross coupling of iodobenzene with tert-butyl
acrylate. The results obtained for dendrimers 6-FeePd to 9-FeePd
are compared with the parent model 5-FeePd and are compara-
tively discussed in terms of the potential ability of the amidoamine
scaffold stabilizing catalytic active palladium species. The
By means of the Hg(0) drop test, reaction mixtures of iodo-
benzene (10), tert-butyl acrylate (11) and 0.5 mol% of 8-FeePd as

S. Dietrich et al. / Journal of Organometallic Chemistry 696 (2011) 739e747
743
Se
PPh2
Se
Ph2P
Fe
Fe
HN
O
O
HN
O
HN
N
O
N
H
O
H
N
O
HN
O
N
H
N
O
N
Fe
Fe
Se
PPh2
Se
Ph2P
HN
NH
O
NH
NH
5-Fe-Se
O
Se
Ph2P
Fe
O
Fe
PPh2
Se
9-Fe-Se
Fig. 2. Seleno-phosphines 5-FeeSe and 9-FeeSe.
(pre)catalyst are quenched with metallic mercury (Fig. 4) at certain
times [30]. Quenching after the catalytically active system is formed
(t ¼ 45 min) extinguishes the catalytic activity instantly, while
adding mercury at the beginning of the catalysis (t ¼ 0 min) even
prevents the formation of a catalytic active palladium species. This
observations of poisoning implies heterogeneous HeckeMizoroki
reactions promoted by Pd(0) particles [31].
3. Conclusions
The preparation and characterization of defined FeePd phosphine
functionalized amidoamines N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe
(h
5-C5H4)(
h
5-C5H4PPh2(Pd(
h
3-C3H5)Cl))))3,
[CH2N(CH2CH2C(O)
5-C5H4PPh2(Pd( 3-C3H5)Cl))))2]2,
5-C5H4))C(O)HNCH2CH2NHC(O)
NHCH2CH2NHC(O)(Fe(
h
h
5-C5H4)(
h
h
(Fe((h
5-C5H4PPh2(Pd(
3-C3H5)Cl))(
h
t
i
O Bu
t
[Pd], NEt Pr2, [CuI]
O Bu
+
I
(1)
toluene / acetonitrile
O
O
10
11
12
100
90
80
70
60
50
40
30
20
10
0
5-Fe-Pd
6-Fe-Pd
7-Fe-Pd
8-Fe-Pd
9-Fe-Pd
0
1
2
3
4
5
6
time / h
Fig. 3. Kinetic investigation of 5-FeePd to 9-FeePd in the HeckeMizoroki carbonecarbon cross-coupling reaction of iodobenzene (10) with tert-butyl acrylate (11) to give E-tert-
butyl cinnamate (12) (0.5 mol% (pre)catalyst; conversion time 0e6 h).

744
S. Dietrich et al. / Journal of Organometallic Chemistry 696 (2011) 739e747
Table 1
were used without further purification. (Diphenylphosphino)ferro-
cenyl carboxylic acid (3) [21b], [Pd(
3-C3H5)Cl]2 (4) [21c] and 5-Fe to
Results of the HeckeMizoroki CeC cross-coupling of iodobenzene with tert-butyl
acrylate by 5-FeePd to 9-FeePd.
h
8-Fe [16e] were prepared according to published procedures.
1H, 13C{1H}, and 31P{1H} NMR spectra were recorded with
Compd.
5-FeePd
6-FeePd
7-FeePd
8-FeePd
9-FeePd
Yield of 12 [%]a
44
88
20
48
96
24
61
122
80
63
126
88
88
176
90
a Bruker Avance III 500 MHz spectrometer. Chemical shifts
d are
TONb
given in ppm (parts per million) using the particular solvent or
H3PO4 as external standard as reference signal. Coupling constants
J are given in Hertz (Hz). IR spectra were recorded with a FT Nicolet
IR 200 instrument in the range of 500e4000 cmꢀ1. The melting
points were obtained using capillaries with an electro thermal
melting point apparatus. Microanalyses were performed with
a C, H, N-analyzer FLASHEA 1112 Series (Thermo Inc.).
TOF [1/h]c
a
Yields are determined by 1H NMR spectroscopy with acetylferrocene as stan-
dard relative to E-tert-butyl cinnamate (12), reaction time 24 h.
b
Mol product/mol [Pd].
Mol product/mol [Pd]/2, determined after 1 h.
c
CH2CH2)N[CH2CH2N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(
-C5H4PPh2(Pd(
3-C3H5)Cl))))2]2, (Fe( 5-C5H4PPh2(Pd(
5-C5H4C(O)NHnC3H7)), and [Fe( 5-C5H4PPh2(Pd( 3-C3H5)Cl))(h5
-
h
5-C5H4)(h5
h
3-C3H5)Cl))
4.2. Preparation of H2NCH2CH2NHC(O)CH2CH2N(CH2CH2N
(CH2CH2C(O)NHCH2CH2NH2)2)2 (2)
h
h
(h
h
h
C5H4C(O)NHCH2)]2, for comparison, using consecutive divergent
growth methodologies including addition, amidation, and complex-
ation reactions is described. These molecules are unique because they
feature as end-grafted moieties heterobimetallic ferrocenyl-based
palladium allyl chlorides. These individual metallodendrimers were
successfully employed as homogeneous Heck catalysts in the vinyl-
ation of iodobenzene with tert-butyl acrylate to give E-tert-butyl
cinnamate. The newly prepared FeePd-catalysts are less active than
the catalyst systems reported earlier with any combination of N-
heterocyclic carbenes [32], bulky electron-rich chelating bis(phos-
phines) [33], palladacycles [34], secondary phosphates or phospho-
nium salts [29a,35], however, the systems prepared show synergistic
and cooperative effects resulting in higher yields and productivities
with increasing numbers of end-grafted FeePd phosphine moieties.
Due to the larger organic matrix with its specific, intrinsic amine
functionalities the amidoamine scaffold with the most immobilized
heterobimetallic ironepalladium features is best suited for the
stabilization of the catalytic active species.
Poly(amidoamine)dendrimer 2 was synthesized by a prepara-
tion procedure firstly described by Tomalia et al. [21a], in a two step
synthesis methodology using 1.0 g (9.7 mmol) of diethylenetri-
amine in 20 mL of methanol. After subsequent addition of methyl
acrylate (10 g, 116 mmol) at 25 ꢁC an excess of ethylenediamine
(33.5 mL, 0.5 mol) was added in a single portion. After 3 days of
stirring all volatiles were evaporated in oil-pump vacuum, whereby
2 was obtained as colorless oil (6.5 g, 99 %, based on diethylene-
triamine). Anal. Calc for C29H63N13O5 (673.9): C, 51.69; H, 9.42; N,
27.02. Found: C, 52.03; H, 9.67; N, 27.19. 1H NMR (
10 H, NH2), 2.37 (m, 10 H, CH2C(O)), 2.56 (br, 8 H, NCH2CH2N), 2.74
d, CDCl3): 1.45 (bs,
3
3
(t, 10 H, JHH ¼ 6.9 Hz, NCH2CH2C(O)), 2.78 (t, 10 H, JHH ¼ 6.3 Hz,
CH2NH2), 3.25 (t, 10 H, 3JHH ¼ 6.3 Hz, NHCH2), 7.66 (m, 5 H, C(O)NH).
13C{1H} NMR (
d, CDCl3): 32.1 (CH2C(O)), 41.3 (NHCH2), 42.3
(CH2NH2), 51.4 (NCH2CH2N), 52.0 (NCH2CH2N), 54.2 (NCH2CH2C
(O)), 168.4 (C(O)). IR (NaCl, cmꢀ1): 3365 (vs, nNH2), 1640 (vs, nC(O)
amide I), 1560 (s, nC(O), amide II).
,
4.3. Preparation of ((Fe(
NHC(O)CH2CH2)N[CH2CH2N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(h5
C5H4)(
5-C5H4PPh2)))2]2 (9-Fe)
h h
5-C5H4PPh2)( 5-C5H4))C(O)HNCH2CH2
4. Experimental
-
h
4.1. Materials and methods
300 mg (0.45 mmol) of 2 in 20 mL of dichloromethane were
mixed with 950 mg (2.3 mmol) of (diphenylphosphino)ferrocenyl
carboxylic acid (3) and 310 mg (2.3 mmol) of HOBT. After stirring for
1 h at 0 ꢁC, 355 mg (2.3 mmol) of EDC in 30 mL of dichloromethane
was slowly added. The resulting reaction mixture was stirred over-
night at 25 ꢁC and afterwards was subsequently washed with 20 mL
of an aqueous solution of ammonium chloride (0.5 M). After drying
the organic layer over MgSO4 the solvents were removed under
reduced pressure. The crude product was purified by column chro-
matography (column size: 10 ꢂ 3 cm, alumina) using dichloro-
methane as eluent. After evaporation of all volatiles in oil-pump
vacuum molecule 9-Fe was obtained as an air stable, orange colored
solid (350 mg, 30 %, based on 2). Mp: 125 ꢁC. Anal. Calc for
C144H148Fe5N13O10P5 (2654.9): C, 65.15; H, 5.62; N, 6.86. Found: C,
Syntheses were performed under a dry and deoxygenated dini-
trogen atmosphere using standard Schlenk techniques unless
otherwise stated. All solvents were carefully dried by standard
procedures over the appropriate drying agents and distilled imme-
diately priortouse.The reagents thatwherepurchased commercially
100
90
80
8-Fe-Pd (Hg)
70
8-Fe-Pd (Hg)
8-Fe-Pd (no Hg)
60
addition of Hg
50
64.63; H, 5.23; N, 6.39. 1H NMR (
d, CDCl3): 2.09 (bs, 20 H, NCH2CH2C
40
30
20
10
0
(O)), 2.51 (m, 8 H, NCH2CH2N), 3.31 (m, 20 H, HNCH2CH2NH), 4.00 (m,
10 H, Ha/C5H4PPh2), 4.07 (m, 10 H, Hb/C5H4C(O)), 4.29 (m, 10 H, Hb/
C5H4PPh2), 4.64 (m, 10 H, Ha/C5H4C(O)), 7.18e7.31 (m, 50 H, C6H5),
7.82 (m, 10 H, NH). 13C{1H} NMR (
d, CDCl3): 29.7 (CH2C(O)), 39.3
(HNCH2CH2NH), 40.4 (HNCH2CH2NH), 50.9 (NCH2CH2C(O)), 51.6
(NCH2CH2N), 51.9 (NCH2CH2N), 69.5 (Ca/C5H4C(O)), 71.9 (Cb/C5H4C
3
2
(O)), 73.1 (d, JCP ¼ 3 Hz, Cb/C5H4C(PPh2)), 74.4 (d, JCP ¼ 13 Hz, Ca/
0
1
2
3
4
5
6
1
C5H4C(PPh2)), 76.6 (Ci/C5H4C(O)), 77.5 (d, JCP ¼ 8 Hz, Ci/C5H4C
time / h
3
(PPh2)), 128.4 (d, JCP ¼ 6 Hz, Cm/C6H5), 128.8 (Cp/C6H5), 133.5 (d,
2JCP ¼ 19 Hz, Co/C6H5), 138.5 (d, 1JCP ¼ 10 Hz, Ci/C6H5), 170.9 (C(O)),
Fig. 4. Hg(0) drop tests of 8-FeePd in the HeckeMizoroki reactions by addition of
metallic mercury at certain times (t ¼ 0 min; t ¼ 45 min) and without the addition of
mercury for comparison.
173.6 (C(O)). 31P{1H} NMR (
d
, CDCl3): ꢀ17.9 (PPh2). IR (KBr, cmꢀ1):
3300 (m, nNH), 1640 (s, nC(O), amide I), 1540 (s, nC(O), amide II).

S. Dietrich et al. / Journal of Organometallic Chemistry 696 (2011) 739e747
745
4.4. Preparation of (Fe(
h
5-C5H4PPh2(Pd(
h
3-C3H5)Cl))(
h
5-C5H4C(O)
7.87 (m, 6 H, NH). 13C{1H} NMR (
d
, CDCl3): 29.9 (NCH2CH2C(O)), 39.6
NHnC3H7)) (5-FeePd)
(HNCH2CH2NH), 39.9 (HNCH2CH2NH), 50.0 (NCH2CH2C(O)), 59.9
(CH2-syn/anti), 69.9 (Ca/C5H4C(O)), 72.4 (Cb/C5H4C(O)), 73.6 (d,
3JCP ¼ 7 Hz, Cb/C5H4C(PPh2)), 73.9 (d, 1JCP ¼ 43 Hz, Ci/C5H4C(PPh2)),
74.5 (d, 2JCP ¼ 15 Hz, Ca/C5H4C(PPh2)), 77.5 (Ci/C5H4C(O)), 118.4 (CH-
centered), 128.3 (d, 3JCP ¼ 10 Hz, Cm/C6H5), 130.3 (Cp/C6H5), 132.7 (d,
2JCP ¼ 12 Hz, Co/C6H5), 135.6 (d, 1JCP ¼ 42 Hz, Ci/C6H5), 170.6 (C(O)),
180 mg (0.4 mmol) of (Fe(
3H7)) (5-Fe) were dissolved in dichloromethane (20 mL) and 75 mg
(0.21 mmol) of [Pd(
3-C3H5)Cl]2 (4) were added in a single portion.
h h
5-C5H4PPh2)( 5-C5H4C(O)NHnC
h
After 1 h of stirring at 25 ꢁC, 5-FeePd was purified by precipitation
from dichloromethane (5 mL) by addition of 20 mL of n-hexane. The
precipitate was washed twice with 10 mL portions of n-hexane.
After appropriate work-up, the title compound was isolated as
a bright yellow solid (230 mg, 90 %, based on 5-Fe). Mp: 150 ꢁC. Anal.
Calc for C29H31ClFeNOPPd (638.3): C, 54.57; H, 4.90; N, 2.91. Found:
171.9 (C(O)). 31P{1H} NMR ( , CDCl3): 12.5 (PPh2). IR (KBr, cmꢀ1):
d
3300 (m, nNH), 1640 (s, nC(O), amide I), 1540 (s, nC(O), amide II), 1480
(w, nh3
-C3H5).
4.7. Preparation of [CH2N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(h5
C5H4)(
5-C5H4PPh2(Pd( 3-C3H5)Cl))))2]2 (8-FeePd)
-
C, 54.44; H, 5.12; N, 2.99.1H NMR(
d
, CDCl3): 0.96(t, 3 H, 3JHH ¼ 7.4 Hz,
h
h
CH3), 1.65 (m, 2 H, CH2CH2CH3), 2.85 (m, 1H, CH-anti), 3.30 (m, 2 H,
CH2CH2CH3), 3.78 (m, 1 H, CH-syn), 4.26 (m, 2 H, Ha/C5H4PPh2), 4.57
(m, 2 H, Hb/C5H4C(O)), 5.02 (m, 2 H, Hb/C5H4PPh2), 5.15 (m, 2 H, Ha/
C5H4C(O)), 5.55 (m,1 H, CH-centered), 7.18 (m,1 H, NH), 7.31e7.78 (m,
The title compound 8-FeePd was synthesized by using
the same synthesis methodology as 5-FeePd, whereby 275 mg
(0.13 mmol) of [CH2N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(
5-C5H4PPh2)))2]2 (8-Fe) were reacted with 100 mg (0.27 mmol)
of [Pd(
3-C3H5)Cl]2 (4). After appropriate work-up, 8-FeePd was
h
5-C5H4)
10 H, C6H5). 13C{1H} NMR (
d, CDCl3): 11.7 (CH3), 23.2 (CH2CH2CH3),
(h
41.5 (CH2CH2CH3), 61.9 (CH2-syn/anti), 70.3 (Ca/C5H4C(O)), 71.9 (Cb/
h
C5H4C(O)), 73.5 (d, 3JCP ¼ 5 Hz, Cb/C5H4C(PPh2)), 74.3 (d,1JCP ¼ 47 Hz,
obtained as a bright yellow solid (240 mg, 65 %, based on 8-Fe). Mp:
2
Ci/C5H4C(PPh2)), 76.4 (d, JCP ¼ 16 Hz, Ca/C5H4C(PPh2)), 78.5 (Ci/
170 ꢁC. Anal. Calc for C126H136Cl4Fe4N10O8P4Pd4 (2833.3): C, 53.41;
C5H4C(O)),118.2 (CH-centered),128.5 (d, 3JCP ¼ 6 Hz, Cm/C6H5),130.2
(Cp/C6H5), 133.1 (d, 2JCP ¼ 12 Hz, Co/C6H5), 135.9 (d, 1JCP ¼ 44 Hz, Ci/
H, 4.84; N, 4.94. Found: C, 53.74; H, 4.96; N, 5.28. 1H NMR (
d, CDCl3):
2.34 (m, 8 H, CH2C(O)), 2.42 (m, 4 H, CH2N), 2.74 (m, 8 H, NCH2CH2C
(O)), 2.84 (m, 4 H, CH-anti), 3.38 (m,16 H, HNCH2CH2NH), 3.81 (m, 4
H, CH-syn), 4.07 (m, 8 H, Ha/C5H4PPh2), 4.28 (m, 8 H, Hb/C5H4C(O)),
4.55 (m, 8 H, Hb/C5H4PPh2), 5.01 (m, 8 H, Ha/C5H4C(O)), 5.61 (m, 4 H,
CH-centered), 7.28e7.78 (m, 40 H, C6H5), 8.18 (m, 8 H, NH). 13C{1H}
C6H5), 169.2 (C(O)). 31P{1H} NMR (
d, CDCl3): 11.6 (PPh2). IR (KBr,
cmꢀ1): 3315 (m, nNH), 1645 (s, nC(O), amide I), 1540 (s, nC(O), amide II),
1480 (w, nh3
-C3H5).
4.5. Preparation of [Fe(
h
5-C5H4PPh2(Pd(
h
3-C3H5)Cl)))(
h
5-C5H4C(O))
NMR (d, CDCl3): 34.8 (CH2C(O)), 39.3 (HNCH2CH2NH), 40.4
NHCH2)]2 (6-FeePd)
(HNCH2CH2NH), 53.5 (NCH2CH2C(O)), 56.7 (CH2N), 61.2 (CH2-syn/
3
anti), 70.4 (Ca/C5H4C(O)), 72.4 (Cb/C5H4C(O)), 73.8 (d, JCP ¼ 7 Hz,
1
Compound 6-FeePd was synthesized in the same manner as
5-FeePd, whereby 150 mg (0.18 mmol) of [Fe(
5-C5H4PPh2)(h5
C5H4C(O)NHCH2)]2 (6-Fe) were reacted with 70 mg (0.2 mmol) of
[Pd(
3-C3H5)Cl]2 (4). After appropriate work-up, 6-FeePd was
Cb/C5H4C(PPh2)), 74.5 (d, JCP ¼ 48 Hz, Ci/C5H4C(PPh2)), 76.2 (Ca/
h
-
C5H4C(PPh2)), 77.9 (Ci/C5H4C(O)), 118.3 (CH-centered), 128.5 (d,
2
3JCP ¼ 10 Hz, Cm/C6H5), 130.4 (Cp/C6H5), 133.1 (d, JCP ¼ 12 Hz, Co/
h
C6H5), 133.6 (d, 1JCP ¼ 48 Hz, Ci/C6H5), 169.9 (C(O)), 170.4 (C(O)). 31
P
obtained as a bright yellow solid (200 mg, 92 %, based on 6-Fe). Mp:
{1H} NMR ( , CDCl3): 13.4 (PPh2). IR (KBr, cmꢀ1): 3300 (m, nNH),1645
d
160 ꢁC. Anal. Calc for C54H52Cl2Fe2N2O2P2Pd2 (1218.4): C, 53.23; H,
(s, nC(O), amide I), 1535 (s, nC(O), amide II), 1480 (w, nh3
-C3H5).
4.30; N, 2.30. Found: C, 53.46; H, 4.31; N, 2.20. 1H NMR (
d, CDCl3):
2.67 (m, 2H, CH-anti), 3.59 (m, 4 H, CH2), 3.86 (m, 2 H, CH-syn), 4.03
(m, 4 H, Ha/C5H4PPh2), 4.27 (m, 4 H, Hb/C5H4C(O)), 4.44 (m, 4 H, Hb/
C5H4PPh2), 4.80 (m, 4 H, Ha/C5H4C(O)), 5.68 (m, 2 H, CH-centered),
4.8. Preparation of (Fe((
h
5-C5H4PPh2(Pd(
h
h
3-C3H5)Cl))( 5-C5H4))C
(O)HNCH2CH2NHC(O)CH2CH2)N[CH2CH2N(CH2CH2C(O)
NHCH2CH2NHC(O)(Fe(
h
5-C5H4)( 5-C5H4PPh2(Pd(
h
h
3-C3H5)Cl))))2]2
7.12 (m, 2 H, NH), 7.38e7.71 (m, 20 H, C6H5). 13C{1H} NMR (
d
, CDCl3):
(9-FeePd)
40.6 (CH2), 61.7 (CH2-syn/anti), 70.2 (Ca/C5H4C(O)), 72.6 (Cb/C5H4C
3
(O)), 73.7 (d, JCP ¼ 9 Hz, Cb/C5H4C(PPh2)), 74.5 (d, 1JCP ¼ 44 Hz, Ci/
Dendrimer 9-FeePd was synthesized in the same manner as
5-FeePd, whereby 150 mg (0.06 mmol) of (Fe((
5-C5H4PPh2)(h5
C5H4))C(O)HNCH2CH2NHC(O)CH2CH2)N[CH2CH2N(CH2CH2C(O)
NHCH2CH2NHC(O)(Fe(
5-C5H4)( 5-C5H4PPh2))2]2 (9-Fe) were
reacted with 55 mg (0.15 mmol) of [Pd(
3-C3H5)Cl]2 (4). After
C5H4C(PPh2)), 76.4 (d, 2JCP ¼ 14 Hz, Ca/C5H4C(PPh2)), 77.5 (Ci/C5H4C
h
-
3
(O)), 118.3 (CH-centered), 128.6 (d, JCP ¼ 9 Hz, Cm/C6H5), 130.3 (Cp/
2
1
C6H5), 133.2 (d, JCP ¼ 12 Hz, Co/C6H5), 135.4 (d, JCP ¼ 44 Hz, Ci/
h
h
C6H5), 170.7 (C(O)). 31P{1H} NMR (
d, CDCl3): 11.4 (PPh2). IR (KBr,
h
cmꢀ1): 3315 (m, nNH), 1640 (s, nC(O), amide I), 1535 (s, nC(O), amide II),
appropriate work-up, 9-FeePd was obtained as a bright yellow solid
(180 mg, 85 %, based on 9-Fe). Mp: 170 ꢁC. Anal. Calc for
C159H173Cl5Fe5N13O10P5Pd5 (3569.6): C, 53.50; H, 4.88; N, 5.10.
1485 (w, nh3
-C3H5).
4.6. Preparation of N(CH2CH2C(O)NHCH2CH2NHC(O)(Fe(
h
5-C5H4)
Found: C, 54.02; H, 4.75; N, 5.43. 1H NMR (
d, CDCl3): 2.31 (m, 20 H,
(h
5-C5H4PPh2(Pd( 3-C3H5)Cl))))3 (7-FeePd)
h
NCH2CH2C(O)), 2.58 (m, 8 H, NCH2CH2N), 2.76 (m, 5 H, CH-anti), 3.31
(m, 20 H, HNCH2CH2NH), 3.79 (m, 5 H, CH-syn), 4.04 (m, 10 H, Ha/
C5H4PPh2), 4.28 (m,10 H, Hb/C5H4C(O)), 4.53 (m,10 H, Hb/C5H4PPh2),
5.01 (m,10 H, Ha/C5H4C(O)), 5.62(m, 5H, CH-centered), 7.27e7.76 (m,
Compound 7-FeePd was synthesized in the same way as
5-FeePd, whereby 140 mg (0.09 mmol) of N(CH2CH2C(O)
NHCH2CH2NHC(O)(Fe(
5-C5H4)( 5-C5H4PPh2)))3 (7-Fe) were reac-
ted with 50 mg (0.135 mmol) of [Pd(
3-C3H5)Cl]2 (4). After appro-
h
h
50 H, C6H5), 7.89 (m, 10 H, NH). 13C{1H} NMR (
d, CDCl3): 34.6 (CH2C
h
(O)), 39.5 (HNCH2CH2NH), 40.1 (HNCH2CH2NH), 50.9 (NCH2CH2C
(O)), 53.5 (CH2N), 61.3 (CH2-syn/anti), 70.3 (Ca/C5H4C(O)), 72.5 (Cb/
C5H4C(O)), 73.9 (d, 3JCP ¼ 7 Hz, Cb/C5H4C(PPh2)), 74.5 (d,1JCP ¼ 46 Hz,
Ci/C5H4C(PPh2)), 77.2 (Ca/C5H4C(PPh2)), 77.8 (Ci/C5H4C(O)), 118.4
(CH-centered),128.5 (d, 3JCP ¼ 11 Hz, Cm/C6H5),130.4 (Cp/C6H5),133.2
priate work-up, 7-FeePd was obtained as a bright yellow solid
(165 mg, 88 %, based on 7-Fe). Mp: 165 ꢁC. Anal. Calc for
C93H99Cl3Fe3N7O6P3Pd3 (2096.9): C, 53.27; H, 4.76; N, 4.68. Found:
C, 53.13; H, 4.91; N, 4.52. 1H NMR (
d, CDCl3): 2.37 (m, 6 H, CH2C(O)),
2
1
2.72 (m, 6 H, NCH2CH2C(O)), 2.97 (m, 3 H, CH-anti), 3.43 (bs, 12 H,
HNCH2CH2NH), 3.84 (m, 3 H, CH-syn), 4.01 (m, 6 H, Ha/C5H4PPh2),
4.29 (m, 6 H, Hb/C5H4C(O)), 4.53 (m, 6 H, Hb/C5H4PPh2), 4.99 (m, 6 H,
Ha/C5H4C(O)), 5.64 (m, 3 H, CH-centered), 7.29e7.81 (m, 30 H, C6H5),
(d, JCP ¼ 11 Hz, Co/C6H5), 133.4 (d, JCP ¼ 44 Hz, Ci/C6H5), 170.0 (C
(O)),170.8 (C(O)). 31P{1H} NMR (
3295 (m, nNH),1640 (s, nC(O), amide I),1540 (s, nC(O), amide II),1480 (w,
nh3
d
, CDCl3): 13.3 (PPh2). IR (KBr, cmꢀ1):
-C3H5).

746
S. Dietrich et al. / Journal of Organometallic Chemistry 696 (2011) 739e747
4.9. Preparation of (Fe(
h
5-C5H4(PPh2(Se))(
h
5-C5H4C(O)NHnC3H7)))
Acknowledgement
(5-FeeSe)
This study was generously supported by the State of Saxony
(Landesgraduierten Stipendium), the EdgareHeinemann-Fellow-
ship of the TU Chemnitz, the Deutsche Forschungsgemeinschaft,
and the Fonds der Chemischen Industrie.
Fifty milligrams (0.11 mmol) of (Fe(h h
5-C5H4PPh2)( 5-C5H4C(O)
NHnC3H7)) (5-Fe) were dissolved in 10 mL of dichloromethane and
8 mg (0.11 mmol) of selenium were added in a single portion. After
1 h of stirring at 25 ꢁC, the suspension was filtered through a pad of
Celite. After evaporation the title compound could be isolated as an
orange solid (55 mg, 98 %, based on 5-Fe). Anal. Calc for
C26H26FeNOPSe (534.3): C, 58.45; H, 4.91; N, 2.62. Found: C, 58.16;
References
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H, 5.22; N, 2.54. 1H NMR (
d
, CDCl3): 0.97 (t, 3 H, 3JHH ¼ 7.3 Hz, CH3),
1.67 (m, 2 H, CH2CH2CH3), 3.33 (m, 2 H, CH2CH2CH3), 3.92 (m, 2 H,
Ha/C5H4PPh2), 4.24 (m, 2 H, Hb/C5H4C(O)), 4.62 (m, 2 H, Hb/
C5H4PPh2), 4.89 (m, 2 H, Ha/C5H4C(O)), 7.39 (m, 1 H, NH), 7.45e7.68
(m, 10 H, C6H5). 13C{1H} NMR
(d, CDCl3): 11.8 (CH3), 23.2
(CH2CH2CH3), 41.4 (CH2CH2CH3), 71.2 (Ca/C5H4C(O)), 71.5 (Cb/C5H4C
(O)), 73.4 (d, 3JCP ¼ 10 Hz, Cb/C5H4C(PPh2)), 75.1 (d, 2JCP ¼ 12 Hz, Ca/
C5H4C(PPh2)), 75.5 (d, 1JCP ¼ 88 Hz, Ci/C5H4C(PPh2)), 79.1 (Ci/C5H4C
3
(O)), 128.4 (d, JCP ¼ 12 Hz, Cm/C6H5), 131.7 (Cp/C6H5), 132.1 (d,
1JCP ¼ 11 Hz, Ci/C6H5), 133.2 (d, Co/C6H5), 169.1 (C(O)). 31P{1H} NMR
(d
, CDCl3): 30.9 1J(
1645 (s, nC(O), amide I), 1540 (s, nC(O), amide II), 560 (s, nP(Se)).
¼ 720 Hz). IR (KBr, cmꢀ1): 3300 (m, nNH),
31Pe77Se)
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4.10. Preparation of (Fe((
HNCH2CH2NHC(O)CH2CH2)N[CH2CH2N(CH2CH2C(O)NHCH2CH2NHC
(O)(Fe(
5-C5H4)( 5-C5H4(PPh2(Se)))))2]2 (9-FeeSe)
h h
5-C5H4PPh2(Se))( 5-C5H4))C(O)
h
h
(b) K. Vassilev, S. Turmanova, M. Dimitrova, S. Boneva, Eur. Polym. J. 45 (2009)
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Organometallics 22 (2003) 4490;
Compound 9-FeeSe was synthesized as described for 5-FeeSe
using 55 mg (0.02 mmol) of (Fe((
5-C5H4PPh2)( 5-C5H4))C(O)
HNCH2CH2NHC(O)CH2CH2)N[CH2CH2N(CH2CH2C(O)NHCH2CH2NH-
C(O)(Fe(
5-C5H4)( 5-C5H4PPh2)))2]2 (9-Fe) and 8 mg (0.11 mmol) of
h
h
h
h
selenium. After appropriate work-up, compound 9-FeeSe was
obtained as an air stable, orange colored solid (50 mg, 85 %, based on
9-Fe). Anal. Calc for C144H148Fe5N13O10P5Se5 (3049.7): C, 56.71; H,
4.89; N, 5.97. Found: C, 56.31; H, 4.94; N, 6.02.1H NMR (
d, CDCl3): 2.03
(m, 20 H, NCH2CH2C(O)), 2.67 (m, 8 H, NCH2CH2N), 3.47 (m, 20 H,
HNCH2CH2NH), 4.15 (m, 10 H, Ha/C5H4PPh2), 4.32 (m, 10 H, Hb/C5H4C
(O)), 4.59 (m, 10 H, Hb/C5H4PPh2), 4.88 (m, 10 H, Ha/C5H4C(O)),
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5553.
7.45e7.67 (m, 50 H, C6H5), 7.72 (m,10 H, NH).13C{1H} NMR (
d, CDCl3):
29.8 (CH2C(O)), 39.7 (HNCH2CH2NH), 40.5 (HNCH2CH2NH), 50.3
(NCH2CH2C(O)), 51.6 (NCH2CH2N), 51.9 (NCH2CH2N), 70.1 (Ca/C5H4C
(O)), 72.1 (Cb/C5H4C(O)), 73.7 (d, 3JCP ¼ 8 Hz, Cb/C5H4C(PPh2)), 75.4 (d,
2JCP ¼ 11 Hz, Ca/C5H4C(PPh2)), 75.6 (d, 1JCP ¼ 88 Hz, Ci/C5H4C(PPh2)),
78.2 (Ci/C5H4C(O)), 128.3 (d, 3JCP ¼ 12 Hz, Cm/C6H5), 131.5 (Cp/C6H5),
132.2 (d, 1JCP ¼ 11 Hz, Ci/C6H5), 133.2 (Co/C6H5), 170.1 (C(O)), 173.2 (C
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d
, CDCl3): 30.7 (1J(31Pe77 ¼ 723 Hz). IR (KBr,
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560 (s, nP(Se)).
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