Water-soluble aminomethyl(ferrocenylmethyl)phosphines and their trinuclear transition metal complexes

Article abstract of DOI:10.1016/S0277-5387(02)01168-3

Reactions of bis(hydroxymethyl)ferrocenylmethylphosphine (1) with amino acids (o-aminobenzoic acid, potassium glycinate and 5-aminoisophthalic acid) lead to the metal-containing phosphino amino acids 1,3-bis(carboxymethyl)-5-(ferrocenylmethyl)-1,3- diaza-

Full text of DOI:10.1016/S0277-5387(02)01168-3

Polyhedron 21 (2002) 2251Á2256
/
www.elsevier.com/locate/poly
Water-soluble aminomethyl(ferrocenylmethyl)phosphines and their
trinuclear transition metal complexes
Andrey A. Karasik b,*, Roman N. Naumov b, Rene´ Sommer a, Oleg G. Sinyashin b,
Evamarie Hey-Hawkins a,*
a Institut fur Anorganische Chemie der Universitat Leipzig, Johannisallee 29, D-04103 Leipzig, Germany
¨
¨
b A.E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Kazan Scientific Center,
Arbuzov str. 8, Kazan 420088, Russian Federation
Received 8 April 2002; accepted 22 July 2002
Abstract
Reactions of bis(hydroxymethyl)ferrocenylmethylphosphine (1) with amino acids (o-aminobenzoic acid, potassium glycinate and
5-aminoisophthalic acid) lead to the metal-containing phosphino amino acids 1,3-bis(carboxymethyl)-5-(ferrocenylmethyl)-1,3-
diaza-5-phosphacyclohexane (2), bis(o-carboxyphenylaminomethyl)ferrocenylmethylphosphine (3), and 1,5-bis(meta-dicarboxy-
phenyl)-3,7-bis(ferrocenylmethyl)-1,5-diaza-3,7-diphosphacyclooctane (4), respectively. Water-soluble trinuclear complexes 5 and 6
were obtained by complexation of 4 with [MCl2(cod)] (Mꢀ
/
Pt, Pd; codꢀ
/
cyclooctadiene) in DMF. Compounds 1Á6 were
/
characterized by multinuclear NMR and IR spectroscopy and microanalysis.
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Ferrocenylmethylphosphine; Phosphino amino acids; 1,3-Diaza-5-phosphacyclohexane; 1,5-Diaza-3,7-diphosphacyclooctane; Water-
soluble complexes; Trinuclear complexes
1. Introduction
reactions of various primary phosphines, formaldehyde
and amino acids were shown to be a powerful method
for the preparation of air-stable, water-soluble phosphi-
The recently obtained ferrocenylmethylphosphine
[1,2] and bis(hydroxymethyl)(ferrocenylmethyl)phos-
phine (1) [3] are relatively rare examples of highly stable
metal-containing phosphines. These compounds belong
to the class of ferrocenylphosphines with a carbon
spacer between the phosphino group and the ferrocene
no amino acids [9Á16], which are a promising basis for
/
the design of homogeneous catalysts that are immobi-
lized in an aqueous second phase.
Here we report the synthesis of some novel metal-
containing phosphino amino acids on the basis of
bis(hydroxymethyl)(ferrocenylmethyl)phosphine
(1)
component [3Á7]. The ability of this type of organome-
/
and two water-soluble heterotrinuclear complexes of
1,5-bis(meta -dicarboxyphenyl)-3,7-bis(ferrocenyl-
methyl)-1,5-diaza-3,7-diphosphacyclooctane.
tallic compound to form bi- and polynuclear complexes,
as well as their catalytic activity in various organic
reactions, are under investigation [8]. However, little is
known about their reactivity in Mannich-type reactions.
It was shown that bis(dimethylaminomethyl)(ferroce-
nylmethyl)phosphine is readily formed in the reaction of
1 with dimethylamine in good yield, but this product
was readily oxidized to the corresponding phosphine
oxide in air [3]. On the other hand, Mannich-type
2. Results and discussion
a-Amino acids exist in a betaine form and are active
in condensation reactions only under basic conditions.
At the same time it has been shown that the main type of
phosphino amino acids formed from their salts by
reaction with bis(hydromethyl)phosphines and formal-
dehyde are heterocyclic 1,3-diaza-5-phosphacyclohex-
* Corresponding authors. Tel.: ꢁ
9739-319
E-mail address: hey@rz.uni-leipzig.de (E. Hey-Hawkins).
/49-341-9736-151; fax: ꢁ49-341-
/
0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 1 6 8 - 3

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A.A. Karasik et al. / Polyhedron 21 (2002) 2251Á2256
/
anes [14]. Reaction of bis(hydroxymethyl)(ferrocenyl-
methyl)phosphine (1) [3] with 2 equiv. of glycine in the
presence of 2 equiv. of KOH and 1 equiv. of parafor-
maldehyde gives the corresponding 1,3-diaza-5-phos-
signals of the desired products were accompanied by
those of the phosphine oxides.
The stability of aminobenzoic acid derivatives is
usually higher than that of a-amino acids [14Á
/
16]. It
ð1Þ
phacyclohexane 2 (Eq. (1)).
was recently established that the type of amino acid used
in the condensation reaction with primary phosphines
and formaldehyde determines the type of phosphino
amino acid that is formed regardless of the stoichiome-
try of the reagents, i.e. primary phosphine, formalde-
hyde and amino acid [15,16]. For example, for o-
Although the 31P chemical shift of 2 (in CD3OD) is to
lower field than expected for diazaphosphacyclohexanes
[14], the presence of this type of heterocycle was
established on the basis of the 1H and 13C NMR
spectra. Well-identified signals of the protons and the
carbon atom of the NÃ
all other groups confirmed the structure of 2.
In the 31P NMR spectrum in 10% aqueous solution of
/
CH2Ã
/
N fragment and signals for
aminobenzoic
acid
bis(o-carboxyphenylamino-
methyl)phosphines are the predominant products, even
when an excess of formaldehyde is employed in the
reaction [9,10,15]. Thus, the reaction of 1 with 2 equiv.
of o-aminobenzoic acid leads as expected to the open-
chain product 3, even when an excess of CH2O is
employed in the formation of 1 from (ferrocenyl-
NaOH only a very broad signal at about ꢂ55 ppm was
observed together with sharp, intense signals at 35.6 and
1.7 ppm, which probably correspond to products of
/
hydrolysis of the CÃ/N bond and oxidation, and thus
ð2Þ
indicate some instability of 2 in water.
methyl)phosphine (Eq. (2)).
Oxidation in the course of a Mannich-type reaction of
1 was observed earlier with dimethylamine [3] and by us
with optically active (S)-a-phenylglycine and (S)-1-
methylbenzylamine. In the 31P NMR spectra of the
reaction mixtures and products isolated as powders the
Compound 3 was isolated as a yellow microcrystalline
solid. The 31P NMR chemical shifts of 3 in methanol
and DMF are similar and comparable to those of
previously reported bis(arylaminomethyl)phenylpho-
1
sphines [9,15]. The H and 13C NMR spectra of 3 are
in accordance with the open-chain structure. The

A.A. Karasik et al. / Polyhedron 21 (2002) 2251Á
/2256
2253
protons of the PÃ
/
CH2Ã
/
N and PÃ
/
CH2Ã
/
Fc fragments
N
signals for the substituted cyclopentadienyl rings, four
signals for the aryl carbon atoms and a singlet for the
carboxyl groups. 1H NMR data provide additional
information about the conformational behavior of
give rise to broad singlets, in contrast to the PÃ
/
CH2Ã
/
groups of the previously obtained analogues, for which
two doublets of doublets were observed due to inequi-
valence of the two prochiral hydrogen atoms [15].
In the presence of at least 2 equiv. of potassium or
sodium hydroxide, 3 is soluble in water (up to 1 M). The
31P NMR signal of the salt solution is broadened and
slightly shifted upfield relative to neutral 3 in DMF
solution. 1H NMR signals in D2O/NaOD are also
broad, but are generally similar to those in DMF
solution.
heterocyclic phosphines. The protons of the PÃ
/
CH2Ã
/
N methylene group form an ABX spin system (two
doublets of doublets) with a notable difference in the
values of the PÃ
/
H coupling constants (2J(PHA) approxi-
mately 5 Hz, 2J(PHB) approximately 9 Hz). This pattern
is typical of diazadiphosphacylooctanes in a crown
conformation with diaxial orientation of the phosphorus
lone pairs [17Á19], that is, the ferrocenylmethyl sub-
/
It was shown previously that bis(hydroxymethyl)-
phosphines react with primary aryl- and benzylamines
(2:2) with the formation of crystalline, air- and moist-
stituents on the phosphorus atoms and the meta-
dicarboxyphenyl groups on the nitrogen atoms do not
change the conformational behavior of diazadiphos-
phacyclooctanes.
The NMR data of 4 in 10% aqueous solutions of
NaOH are quite similar to those of 4 in DMF.
Deprotonation of the carboxyl groups results in a
ure-stable 1,5-diaza-3,7-diphosphacyclooctanes [17Á
which can be used as bidentate chelate diphosphine
ligands for various transition metals [20Á22]. However,
/19],
/
water-soluble derivatives were obtained only with p-
aminobenzoic acid as primary amine and oxymethyl
derivatives of o-phosphinophenols [15]. Therefore, a
more hydrophilic amine should be used to obtain water-
soluble 3,7-bis(ferrocenylmethyl)-1,5-diaza-3,7-diphos-
phacyclooctane ligands. Heating of 1 with 5-aminoi-
sophthalic acid in boiling ethanol resulted in the
formation of yellow, microcrystalline, air-stable 1,5-
high-field shift of the aryl and PÃ
the H NMR spectrum. No evidence of oxidation or
hydrolysis was observed in aqueous solutions.
/
CH2Ã
/
N signals in
1
When 4 is treated with [MCl2(cod)] (Mꢀ
codꢀ
cyclooctadiene) in DMF, the 31P NMR spectrum
of the reaction mixture shows a signal downfield relative
/
Pt, Pd;
/
to 4 (Ddꢀ
/
44.1 (Mꢀ
/
Pt) and 61.1 ppm (Mꢀ/Pd)) with
ð3Þ
bis(meta-dicarboxyphenyl)-3,7-bis(ferrocenylmethyl)-
1,5-diaza-3,7-diphosphacyclooctane (4) (Eq. (3)).
The IR spectrum of 4 exhibits strong absorptions for
the carboxyl groups (1596, 1698, and 3440 cmꢂ1). In the
31P NMR spectrum only one signal is observed in the
satellites due to coupling with 195Pt nuclei. The PtÃ
coupling constant of 3064 Hz indicates the formation of
the cis-P,P chelate trinuclear complexes 5 and 6 [22]
(Eq. (4)).
/P
The IR spectra of 5 and 6 exhibit strong absorptions
for carboxyl groups (1590Á
1720 and 3430 cmꢂ1) and
also absorption bands of the backbone vibrations of
characteristic region for 1,5-diaza-3,7-diphosphacy-
1
/
clooctanes [15,17Á
/
19]. The 13C and H NMR spectra
of 4 are consistent with the heterocyclic phosphine
structure [15,17Á
19]. The 13C NMR spectrum shows
signals for the PÃCH2ÃN and PÃCH2ÃFc methylene
groups, one signal for the cyclopentadienyl rings, three
heterocycles.
The 13C and 1H NMR spectra are consistent with the
structure and are in general similar to that of 4. In the
/
/
/
/
/
1H NMR spectra only the signal of the PÃ
/
CH2Ã/Fc

2254
A.A. Karasik et al. / Polyhedron 21 (2002) 2251Á2256
/
ð4Þ
1
methylene groups of 5 and 6 change dramatically. These
signals are shifted downfield (Dd Â1.2Á1.5 ppm) and
overlap with those of the PÃCH2ÃN fragment. Due to
tra: Avance DRX 400 (Bruker), standards: H NMR
(400 MHz): internal solvent; 13C NMR (100.6 MHz):
internal solvent; 31P NMR (162 MHz): external 85%
H3PO4. The IR spectra were recorded as KBr mulls on a
/
/
/
/
this overlap it is impossible to establish the conforma-
tion of 5 and 6 in solution. In the 13C NMR spectra, the
PerkinÁ
range 350Á
/
Elmer FT-IR spectrometer System 2000 in the
4000 cmꢂ1. The m.p. were determined in
signal of the PÃ
/
CH2Ã/Fc methylene group is situated in
/
the usual region.
sealed capillaries and are uncorrected.
Bis(hydroxymethyl)(ferrocenylmethyl)phosphine (1)
was obtained according to a literature procedure [3].
The trinuclear complexes 5 and 6 are readily soluble
in water in the presence of at least 4 equiv. of base
(NaOH). The deprotonation and change of solvent
cause a high-field shift of the 13P NMR signal (Ddꢀ
/
ꢂ
/
6.2 ppm) and a decrease in the PtÃ
/
P coupling
4.1.1. 1,3-Bis(carboxymethyl)-5-(ferrocenylmethyl)-
1,3-diaza-5-phosphacyclohexane (2)
constant for 5 (Dꢀ
solution were previously observed for tertiary phosphi-
1
no amino acids [15], including 4. The H NMR signals
/
85 Hz). High-field shifts in aqueous
To a suspension of 1 (0.75 g, 2.6 mmol) were added
glycine (0.39 g, 5.2 mmol) and paraformaldehyde (0.08
g, 2.7 mmol) in 3 ml of MeOH and 2.8 ml of 10% KOH
(5.3 mmol) in MeOH, and the reaction mixture was
stirred for 24 h. The yellow microcrystalline solid which
formed was filtered off, washed with MeOH and dried
of the PÃ
/
CH2Ã/N methylene groups are slightly shifted
to low-field relative to 4.
Studies on the coordination chemistry of 2, 3 and 4
are in progress.
under vacuum. Yield: 0.62 g (38%); m.p. ꢀ250 8C
/
(dec.). Anal. Calc. for C18H25FeK2N2O6P [530.42]: C,
40.8; H, 4.8; N, 5.3; P, 5.9. Found: C, 40.3; H, 4.5; N,
5.4; P, 6.1%.
3. Conclusions
A number of water-soluble open-chain and cyclic
phosphino amino acids containing ferrocenylmethyl
moieties was obtained via a Mannich-type condensation
reaction of bis(hydroxymethyl)ferrocenylmethylpho-
sphine with potassium glycinate, o-aminobenzoic acid
and 5-aminoisophthalic acid. The water-soluble trinuc-
lear Fe2Pt and Fe2Pd complexes were synthesized and
characterized spectroscopically.
1H NMR (MeOH-d4): d 2.99 (s, br, 2H, PÃ
3.28Á3.30 (m, 4H, PÃCH2Ã
CO2), 4.05 (d, JHH
12.0 Hz, 1H, NÃ
br, 2H, C5H4ÃH3 (for numbering scheme see Eq. (1))),
4.12 (s, 5H, C5H5), 4.16 (d, JHH
12.0 Hz, 1H, NÃ
CH2AÃ
N), 4.19 (s, 2H, C5H4ÃH2), 4.83 (s, 4H, H2O).
13C{1H} NMR (MeOH-d4): d 18.7 (s, br, PÃ
CH2ÃFc),
60.7 (s, br, PÃCH2ÃN), 68.8 (s, C5H4ÃC3), 69.9 (s,
C5H5), 70.0 (s, C5H4ÃC2), 76.4 (s, NÃCH2ÃN), 84.7 (s,
br, C5H4Ã
C1), 174.1 (s, CO2H). 31P{1H} NMR (MeOH-
d4): d ꢂ
50.0; 31P{1H} NMR (10% NaOH in D2O): d
55 (s, br). IR (n˜ H2O),
/cmꢂ1, KBr): 1599, 1630 (COꢁ
3424 (HO).
/
CH2Ã
N), 3.41 (s, 4H, NÃCH2Ã
CH2BÃ
N), 4.06 (s,
/
Fc),
/
/
/
/
/
ꢀ
/
/
/
/
ꢀ
/
/
/
/
/
/
/
/
/
/
/
/
/
4. Experimental
/
ꢂ
/
/
/
/
4.1. General considerations
All manipulations were carried out with standard
high-vacuum and dry-nitrogen techniques. NMR spec-

A.A. Karasik et al. / Polyhedron 21 (2002) 2251Á
/2256
2255
4.1.2. Bis(o-carboxyphenylaminomethyl)-
ferrocenylmethylphosphine (3)
31P{1H} NMR (10% NaOH in D2O): d ꢂ
n˜ aryl), 3440 (HO).
/cmꢂ1, KBr): 1596, 1698 (COꢁ
/
54.6 (s). IR
(/
/
/
A solution of 1 (0.77 g, 2.6 mmol) and anthranilic acid
(0.72 g, 5.2 mmol) in 15 ml of MeOH was stirred for 24
h. The solvent was removed under vacuum, and the
yellow powder was washed with Et2O, collected by
filtration and dried under vacuum. Yield: 1.00 g (72%);
4.1.4. cis-{P,P-1,5-Bis(meta-dicarboxyphenyl)-3,7-
bis(ferrocenylmethyl)-1,5-diaza-3,7-
diphosphacyclooctane}dichloroplatinum(II) (5)
[PtCl2(cod)] (0.18 g, 0.5 mmol) was added to a
solution of 4 (0.41 g, 0.5 mmol) in 15 ml of DMF, and
the reaction mixture was stirred for 24 h. The solvent
was removed in vacuum, and the yellow microcrystalline
solid was washed with Et2O, collected by filtration and
m.p. ꢀ250 8C (dec.). Anal. Calc. for C27H27FeN2O4P
/
[530.34]: C, 61.1; H, 5.1; N, 5.3; P, 5.8. Found: C, 60.9;
H, 5.3; N, 5.1; P, 5.6%.
1H NMR (DMF-d7): d 3.04 (s, br, 2H, PÃ
/
CH2Ã
/
Fc),
H9
3.71 (s, br, 4H, PÃ
/
CH2Ã
/
N), 4.24 (s, br, 2H, C5H4Ã
/
dried under vacuum. Yield: 0.30 g (52%); m.p. ꢀ
/
(for numbering scheme see Eq. (2))), 4.29 (s, 5H, C5H5),
250 8C (dec.). Anal. Calc. for C42H40Cl2Fe2N2O8P2Pt
[1140.42]: C, 44.2; H, 3.5; N, 2.4; P, 5.4. Found: C, 43.8;
H, 3.8; N, 2.3; P, 5.2%.
4.34 (s, br, 2H, C5H4Ã
/
H8), 6.76 (dd, 3JHH
ꢀ
/
7.8, 3JHH
8.3 Hz, 2H,
7.3 Hz, 2H,
7.83 Hz, 2H, C6H4ÃH3),
13.0 (s, br, 2H, CO2H). 13C{1H} NMR (DMF-d7): 24.8
(d, 1JPC Fc), 39.6 (d, 1JPC
16.5 Hz, PÃCH2Ã 14.5 Hz,
PÃCH2ÃN), 68.1 (s, C5H4ÃC9), 69.4 (s, C5H5ꢁC5H4Ã
C8), 84.4 (s, br, C5H4ÃC7), 111.4 (s, C6H4ÃC6), 112.5
(s, C6H4ÃC2), 115.2 (s, C6H4ÃC4), 132.5 (s, C6H4ÃC3),
135.0 (s, C6H4ÃC5), 152.1 (s, br, C6H4ÃC1), 171.1 (s,
CO2H). 31P{1H} NMR (DMF-d7): d ꢂ30.0 (s); 31P{1H}
NMR (10% NaOH in D2O): d ꢂ35.4 (s, br). IR (n˜
cmꢂ1, KBr): 1590Á
1720 (COꢁaryl), 3500 (HO, NH).
ꢀ
/
2
7.3 Hz, 2H, C6H4Ã
/
H4) 7.04 (d, JHH
ꢀ
ꢀ
/
3
3
C6H4Ã
/
H6), 7.52 (m, JHH
H5), 8.07 (d, JHH
ꢀ
/
8.3, JHH
/
1H NMR (DMF-d7): d 3.99Á
/
4.04 (m, 8H, PÃ
N), 4.17 (d, JHH
15.6 Hz, 4H, PÃ
N) 4.23 (s, 10H, C5H5), 4.26 (s, 4H, C5H4ÃH7
(for numbering scheme see Eq. (4))), 4.68 (s, 4H, C5H4Ã
H6), 7.74 (s, 4H, C6H3ÃH2), 8.17 (s, 2H, C6H3ÃH4),
13.5 (s, br, 4H, CO2H); 1H NMR (10% NaOH in D2O):
d 2.04 (s, 4H, PÃCH2ÃFc), 3.31 (m, 4H, PÃ N),
CH2AÃ
14.4, 4H, PÃ N), 3.88 (s, 4H,
CH2BÃ
H7), 4.06 (s, 10H, C5H5), 4.19 (s, 4H, C5H4Ã
/
CH2Ã
/
3
2
C6H4Ã
/
ꢀ
/
/
Fcꢁ
/
PÃ
/
CH2AÃ
/
ꢀ
/
/
CH2BÃ
/
/
ꢀ
/
/
/
ꢀ
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
2
/
/
3.64 (d, JHH
ꢀ
/
/
/
/
C5H4Ã
/
/
H6),
H4).
/
/
//
7.18 (s, 4H, C6H5Ã
/
H2), 7.66 (s, 2H, C6H5Ã
/
1
/
/
13C{1H} NMR (DMF-d7): d 22.5 (d, JPC
ꢀ
/
24.8 Hz,
N), 69.4
1
PÃ
(s, C5H4Ã
br, C5H4Ã
133.1 (s, C6H3Ã
/
CH2Ã
/
Fc), 46.7 (d, JPC
ꢀ
/
36.0 Hz, PÃ
/
CH2Ã
C6), 80.2 (s,
C2), 122.7 (s, C6H3ÃC4),
C1), 167.4 (s,
/
/
C7), 69.7 (s, C5H5), 70.2 (s, C5H4Ã
C5), 122.1 (s, C6H3Ã
C3), 150.9 (s, C6H3Ã
/
4.1.3. 1,5-Bis(meta-dicarboxyphenyl)-3,7-
bis(ferrocenylmethyl)-1,5-diaza-3,7-
diphosphacyclooctane (4)
A solution of 1 (1.42 g, 5 mmol) and 5-aminoi-
sophthalic acid (0.88 g, 5 mmol) in 40 ml of EtOH was
refluxed for 6 h. The resulting yellow crystals were
collected by filtration, washed with EtOH, and dried
/
/
/
/
/
CO2H). 31P{1H} NMR (DMF-d7): d ꢂ
/
9.8 (s with Pt
1
satellites, JPPt
in D2O): d ꢂ
1595, 1644, 1715 (COꢁ
ꢀ
/
3064 Hz); 31P{1H} NMR (10% NaOH
16.0 (1JPPt
/
ꢀ/2979 Hz). IR (/
n˜
/cmꢂ1, KBr):
/
/aryl), 3426 (HO).
under vacuum. Yield: 1.21 g (57%); m.p. ꢀ
/
250 8C
4.1.5. cis-{P,P-1,5-Bis(meta-dicarboxyphenyl)-3,7-
bis(ferrocenylmethyl)-1,5-diaza-3,7-
(dec.). Anal. Calc. for C42H40Fe2N2O8P2 [874.43]: C,
57.7; H, 4.6; N, 3.2; P, 7.1. Found: C, 56.9; H, 4.4; N,
3.4; P, 7.4%.
diphosphacyclooctane}dichloropalladium(II) (6)
[PdCl2(cod)] (0.13 g, 0.5 mmol) was added to a
solution of 4 (0.39 g, 0.5 mmol) in 15 ml of DMF, and
the reaction mixture was stirred for 24 h. The solvent
was removed in vacuum, and the yellow microcrystalline
solid was washed with acetone collected by filtration
1H NMR (DMF-d7): d 2.81 (s, 4H, PÃ
(dd, 2JHH 14, 2JPH CH2AÃ
6.0 Hz, 4H, PÃ
4H, C5H4ÃH7 (for numbering scheme see Eq. (3))), 4.15
(s, 4H, C5H4ÃH6), 4.19 (s, 10H, C5H5), 4.27 (dd,
/
CH2Ã
/
Fc), 3.96
ꢀ
/
ꢀ
/
/
/
N), 4.14 (s,
/
/
2
2JHH
4H, C6H3Ã
ꢀ
/
14.0, JPH
ꢀ
/
13.0 Hz, 4H, PÃ
/
CH2BÃ
/
N), 7.54 (s,
and dried under vacuum. Yield: 0.20 g (42%); m.p. ꢀ
/
/
H2), 7.89 (s, 2H, C6H3Ã
/
H4), 13.3 (s, br, 4H,
CO2H); 1H NMR (10% NaOH in D2O): 2.78 (s, 4H, PÃ
250 8C (dec.). Anal. Calc. for C42H40Cl2Fe2N2O8P2Pd
[1051.73]: C, 47.9; H, 3.8; N, 2.7; P, 5.9. Found: C, 47.3;
H, 4.0; N, 2.4; P, 5.6%.
/
2
Fc), 3.6 (dd, JHH
2
12.0, JPH
CH2Ã
/
ꢀ
/
ꢀ
/
12.0 Hz, 4H, PÃ
/
2
N), 3.8 (dd, JHH
2
12.0, JPH
2
CH2AÃ
/
ꢀ
/
ꢀ
/
2.0 Hz, 4H, PÃ
/
1H NMR (DMF-d7): d 4.11 (d, JHH
ꢀ
/
15.6 Hz, 4H,
Fc), 4.40Á4.45
N), 4.47 (s, 4H, C5H4ÃH7
(for numbering scheme see Eq. (4))), 4.90 (s, br, 4H,
CH2BÃ
/
N), 4.01 (s, 4H, C5H4Ã
/
H7), 4.03 (s, 10H, C5H5),
PÃ
/
CH2AÃ
/
N), 4.23 (s, br, 4H, PÃ
/
CH2Ã
/
/
4.07 (s, 4H, C5H4Ã
/
H6), 7.12 (s, 4H, C6H5Ã
/H2), 7.48 (s,
(m, 14H, C5H5ꢁ
/
PÃ
/
CH2BÃ
/
/
2H, C6H5Ã
PÃCH2Ã
(s, C5H4Ã
br, C5H4Ã
132.4 (s, C6H3Ã
CO2H). 31P{1H} NMR (DMF-d7):
/
H4). 13C{1H} NMR (DMF-d7): d 25.7 (s, br,
1
/
/
Fc), 56.2 (d, JPC
ꢀ
/
18.3 Hz, PÃ
/
CH2Ã
C6), 84.4 (s,
C2), 118.0 (s, C6H3ÃC4),
C3), 146.6 (s, C6H3ÃC1), 168.0 (s,
53.9 (s);
/N), 68.1
C5H4Ã
/
H6), 7.94 (s, 4H, C6H3Ã
/
H2), 8.21 (s, 2H, C6H3Ã
/
/
C7), 69.4 (s, C5H5), 69.5 (s, C5H4Ã
/
H4), 13.6 (s, br, 4H, CO2H). 13C{1H} NMR (DMF-d7):
1
/
C5), 117.6 (s, C6H3Ã
/
/
d 25.2 (s, br, PÃ
CH2ÃN), 69.5 (s, C5H4Ã
C5H4ÃC6), 80.5 (s, br, C5H4Ã
/
CH2Ã
/
Fc), 47.4 (d, JPC
ꢀ
/
31.3 Hz, PÃ
/
/
/
/
/C7), 69.7 (s, C5H5), 70.2 (s,
d
ꢂ
/
/
/
C5), 122.2 (s, C6H3ÃC2),
/

2256
A.A. Karasik et al. / Polyhedron 21 (2002) 2251Á2256
/
(b) M. Ogasawara, K. Yoshida, T. Hayashi, Organometallics 20
(2001) 3913.
[8] R. Sommer, P. Lonnecke, P.K. Baker, E. Hey-Hawkins, Inorg.
¨
122.9 (s, C6H3Ã
C6H3Ã
C1), 167.3 (s, CO2H). 31P{1H} NMR (DMF-
d7): d 7.2 (s). IR (n˜
/cmꢂ1, KBr): 1598, 1650, 1715 (COꢁ
aryl), 3430 (HO).
/
C4), 133.4 (s, C6H3Ã
/
C3), 150.1 (s,
/
/
/
/
Chem. Commun. 5 (2002) 115.
[9] I.O. Georgiev, A.A. Karasik, F.F. Nigmadzyanov, G.N. Niko-
nov, Russ. J. Coord. Chem. 21 (1995) 222.
[10] I.O. Georgiev, A.A. Karasik, G.N. Nikonov, Phosphorus Sulfur
Silicon 111 (1996) 133.
Acknowledgements
[11] A.A. Karasik, I.O. Georgiev, R.I. Vasiliev, O.G. Sinyashin,
Mendeleev Commun. (1998) 140.
Financial support from INTAS (N 00-00677) is
gratefully acknowledged. K.A.A. thanks the Sachsisches
Ministerium fur Wissenschaft und Kunst (SMWK, Az.:
¨
4-7531.50-04-0361-01/11) and DFG (Az.: 436 RUS 17/
60/01) for financial support.
[12] D.E. Berning, K.V. Katty, C.L. Barnes, W.A. Volkert, J. Am.
Chem. Soc. 121 (1999) 1658.
¨
[13] J.G.E. Krauter, M. Beller, Tetrahedron 56 (2000) 771.
[14] A.A. Karasik, I.O. Georgiev, O.G. Sinyashin, E. Hey-Hawkins,
Polyhedron 19 (2000) 1455.
[15] A.A. Karasik, I.O. Georgiev, E.I. Musina, O.G. Sinyashin, J.
Heinicke, Polyhedron 20 (2001) 3321.
[16] O.G. Sinyashin, A.A. Karasik, I.O. Georgiev, S.V. Bobrov, J.
Heinicke, E. Hey-Hawkins, Phosphorus Sulfur 177 (2002), in
press.
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