Clathrochelates meet phosphorus: Thiophosphorylation of Fe(ii) dichloroclathrochelate precursor, synthesis of N,S-donor macrobicyclic ligands and their Pd(ii) complexes as potent catalysts of Suzuki cross-coupling reaction

Article abstract of DOI:10.1039/c3dt53590h

Nucleophilic substitution of an iron(ii) dichloroclathrochelate with diphenylphosphine sulfide under PTC afforded a monophosphorylated cage complex. This precursor undergoes further nucleophilic substitution with mono- and diamines giving P,N-substituted mono- and bis-clathrochelates; those with thiophosphoryl and pyridyl groups were used as N,S-donor macrobicyclic ligands toward the palladium(ii) ion. In the resulting Pd,Fe-binuclear 1:1 complexes, the clathrochelate moieties retain the geometry, characteristic of low-spin iron(ii) complexes, with a minor distortion caused by intramolecular interactions. The Pd²⁺ ion has a twisted square-planar N ₂SCl-environment. The complexes thus obtained proved to be efficient catalysts of the Suzuki cross-coupling reaction.

Full text of DOI:10.1039/c3dt53590h

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PAPER
Clathrochelates meet phosphorus:
thiophosphorylation of Fe(II)
dichloroclathrochelate precursor, synthesis
of N,S-donor macrobicyclic ligands and their
Pd(II) complexes as potent catalysts of Suzuki
cross-coupling reaction†‡§¶
Cite this: Dalton Trans., 2014, 43,
9677
Oleg I. Artyushin,a Irina L. Odinets,a Ekaterina V. Matveeva,a Anna V. Vologzhanina,a
Oleg A. Varzatskii,b Sergey E. Lyubimova and Yan Z. Voloshin*a
Nucleophilic substitution of an iron(II) dichloroclathrochelate with diphenylphosphine sulfide under PTC
afforded a monophosphorylated cage complex. This precursor undergoes further nucleophilic sub-
stitution with mono- and diamines giving P,N-substituted mono- and bis-clathrochelates; those with
thiophosphoryl and pyridyl groups were used as N,S-donor macrobicyclic ligands toward the palladium(II)
ion. In the resulting Pd,Fe-binuclear 1 : 1 complexes, the clathrochelate moieties retain the geometry,
characteristic of low-spin iron(II) complexes, with a minor distortion caused by intramolecular interactions.
The Pd2+ ion has a twisted square-planar N2SCl-environment. The complexes thus obtained proved to be
efficient catalysts of the Suzuki cross-coupling reaction.
Received 20th December 2013,
Accepted 28th March 2014
DOI: 10.1039/c3dt53590h
www.rsc.org/dalton
polymerases,7 and HIV protease8). The latter, for instance,
make them prospective antiviral and antitumor drug can-
Introduction
During the last decade, functionalized cage metal complexes didates (so-called “topological drugs”9).
(clathrochelates1) and the hybrid nanosized molecular and
Ribbed functionalizing substituents in their chelate α-dioxi-
supramolecular systems based on them have been intensively mate fragments affect spatial and electronic structures of the
studied as prospective molecular electronic devices2 and clathrochelate framework and, as a result, chemical reactivity of
sensors,3 very efficient electrocatalysts for hydrogen pro- the caging ligands and redox properties of an encapsulated metal
duction,4 electrochromic materials5, potent targeting com- ion. N,O,S,C-Nucleophilic substitution of the pre-synthesized
pounds for the 10B-NCT treatment of tumor diseases6 and reactive mono- and polyhalogenoclathrochelate precursors is
transcription inhibitors for various enzymes (T7 RNA and DNA reported to be the most convenient and easiest pathway for
such functionalization;10 it has been widely used for the
design of different types of ribbed-functionalized clathro-
chelates and their derivatives. Cage metal complexes with
inherent phosphorus-containing pendant substituents,
aNesmeyanov Institute of Organoelement Compounds of the Russian Academy of
Sciences, 28 Vavilova st., 119991 Moscow, Russian Federation.
E-mail: voloshin@ineos.ac.ru; Tel: +7 499 135 9344
however, have not been reported to date, mostly due to syn-
thetic challenges (see the Results and discussion part). At the
same time, such (thio)phosphorylated cage complexes seem to
be prospective precursors for the design of hybrid and multi-
centered systems with unusual chemical, redox and catalytic
properties.
bVernadskii Institute of General and Inorganic Chemistry of the National Academy of
Sciences of Ukraine, 32/34 Palladina pr., 03680 Kyiv, Ukraine
†Dedicated to the memory of our colleague Prof. I. L. Odinets who passed away
on 26 June, 2012.
‡This title was inspired by a title of the lecture of Prof. E. Hey-Hawkins “Car-
baborane meets phosphorus”, EUROBORON-6, Radziejowice, Poland, 8–13th
September 2013.
Clathrochelates with donor (thio)phosphoryl groups are of
special interest, as such groups can be used to synthesize
various polynuclear systems for practical applications. In par-
ticular, complexes of rare earth metals, scandium(III), copper,
palladium, platinum, zinc and nickel(II) ions with phosphorus-
containing ligands have been used for their selective extraction
§A preliminary account of this work was presented at the 19th International
Conference on Phosphorus Chemistry, Rotterdam, 8–12 July, 2012.
(I. L. Odinets, O. I. Artyushin, E. V. Matveeva, A. V. Vologzhanina and
Y. Z. Voloshin, Phosphorus, Sulfur, Silicon, 2013, 188, 159–161.)
¶Electronic supplementary information (ESI) available: Crystallographic and UV-
vis tables. CCDC 973317–973323. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/c3dt53590h
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and separation11 as well as luminescent materials.12 The palla- the diiodoclathrochelate precursor FeBd2(I2Gm)(BF)2.10i The
dium(II) complexes of functionalized phosphine ligands are plausible mechanism of this reaction includes the formation
also efficient metallocomplex catalysts of the homogenous of clathrochelate anion radicals by a reduction of the precursor
Suzuki and Heck coupling reactions,13 e.g. of aryl halides with with a corresponding phosphine and an abstraction of a
phenylboronic acids14. These cross-coupling reactions are hydrogen atom from a solvent or reactants by these very reac-
among the most powerful methods for CAr–CAr bond for- tive species (Scheme 1).
mation, owing to the commercial availability of such aryl
As a result, we chose the nucleophilic substitution with
halides, their tolerance for a broad range of functionalities, as organophosphorus(V) derivatives for the synthesis of phos-
well as the easy handling of the non-toxic boron-containing by- phorus-containing iron(II) clathrochelates. The most feasible
products. They are very useful on an industrial level, mainly pathway to mono- and difunctionalized thio- and phosphory-
for the synthesis of pharmaceuticals and fine chemicals. The lated iron(II) clathrochelates is based on the stepwise nucleo-
use of cage complexes with redox active encapsulated metallo- philic substitution of their dihalogenoclathrochelate
centers as the donor “building blocks” (i.e. as clathrochelate precursors, with the corresponding phosphorus-containing
ligands) in this case allows the production of electrochemically nucleophiles (Scheme 2). The same reactions with O,N,S,-
operated metallocomplex catalytic systems for homogenous C-nucleophiles have been intensively used for the synthesis of
reactions of this type.
a wide range of monoribbed-functionalized iron and cobalt(II)
In this paper, we describe the synthesis and X-ray structures clathrochelates. We, however, failed to perform such a phos-
of the first phosphorylated clathrochelate, its reactivity in phorylation under the typical conditions of the Arbuzov and
nucleophilic substitution reactions, coordination-chemical Michaelis–Becker reactions (inert solvent and temperature
properties of mixed P,N-substituted ribbed-functionalized cage range 0–150 °C), as a result of the decomposition of the cla-
compounds as macrobicyclic N,S-donor ligands toward palla- throchelate framework dominating under these reaction
dium(II) ion and a catalytic activity of the Pd,Fe-binuclear com- conditions.
plexes obtained in the Suzuki cross-coupling reaction.
As it has been shown earlier,15 switching to phase-transfer
conditions (PTC) is a good choice if the use of the above reac-
tion conditions gives no phosphorylated products. Indeed,
nucleophilic substitution of dichloroclathrochelate precursor
FeBd2(Cl2Gm)(BF)2 with diphenylphosphine sulfide in
Results and discussion
The reactions of the dichloroclathrochelate precursor Scheme 3 under PTC resulted in the formation of monochloro-
FeBd2(Cl2Gm)(BF)2 (where Bd2− and Gm2− are α-benzyldioxime monothiophosphorylated cage complex FeBd2(((C6H5)2P(S))-
and glyoxime dianions, respectively) with organophosphorus(III) ClGm)(BF)2 in high yield even at a 5-fold excess of the thio-
compounds (di- and trialkyl(aryl)phosphines and their phosphorylating agent. This thiophosphorylated iron(II)
halogen-containing derivatives) did not give the target monochloroclathrochelate undergoes no further thiophos-
phosphine cage complexes, but mainly resulted in the phorylation, leading to the dithiophosphorylated complex even
side reduction–hydrodehalogenation processes (Scheme 1), under the typical phosphorylation reaction conditions
affording mono- and dimethine clathrochelate by-products. (Scheme 3); however, these attempts led to the complete
The same reduction–hydrodehalogenation reactions (but with destruction of its clathrochelate framework. This fact may be
copper(I) ion as a reductant) have been earlier described for explained by steric hindrances between the two bulky diphe-
Scheme 1 The plausible mechanism of the reduction–hydrodehalogenation reactions leading to the methine clathrochelates.
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Scheme 2 Most feasible pathway to the thiophosphorylated iron(II) clathrochelates.
Scheme 3 Nucleophilic substitution of dichloroclathrochelate precursor FeBd2(Cl2Gm)(BF)2 with diphenylphosphine sulfide.
nylthiophosphine ribbed substituents in the complex. At the
For the synthesis of its bis-clathrochelate derivative
same time, the monochloroclathrochelate FeBd2(((C6H5)2P(S))- [FeBd2(((C6H5)2P(S))Gm)(BF)2]2(NH(CH2)5NH), two synthetic
ClGm)(BF)2 easily undergoes nucleophilic substitution with strategies were used (Scheme 5): the first one is based on the
sterically unhindered primary and secondary amines under interaction of an excess of this monochloroclathrochelate pre-
mild reaction conditions by Scheme 4, giving P,N-substituted cursor with cadaverine, while the other uses the nucleophili-
monoribbed-functionalized iron(II) cage complexes in high city of the initially synthesized clathrochelate FeBd2(((C6H5)2-
yields.
P(S))(H2N(CH2)5NH)Gm)(BF)2 with a terminal amino group.
Scheme 4 Synthesis of P,N-substituted monoribbed-functionalized iron(II) cage complexes.
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Scheme 5 Synthesis of the thiophosphorylated bis-clathrochelate
[FeBd2(((C6H5)2P(S))Gm)(BF)2]2(NH(CH2)5NH).
Scheme 6 Synthesis of the Pd,Fe-binuclear complexes of N,S-donor
macrobicyclic ligands.
Both these synthetic approaches gave the target bis-clathro-
chelate [FeBd2(((C6H5)2P(S))Gm)(BF)2]2(NH(CH2)5NH) under
mild reaction conditions (room temperature, acetonitrile as a
solvent) in high yields.
(((C6H5)2P(S))(2-NHCH2Py)Gm)(BF)2,
FeBd2(((C6H5)2P(S))-
(CH3SCH2CH2NCH3)Gm)(BF)2 and [FeBd2(((C6H5)2P(S))Gm)-
(BF)2]2(NH(CH2)5NH) as well as the palladium(II) complexes
[Pd-(FeBd2(((C6H5)2P(S))(2-NCH2Py)Gm)(BF)2)Cl] and [Pd(FeBd2-
Two of the complexes obtained (i.e. FeBd2(((C6H5)2P(S))-
(2-NHCH2Py)Gm)(BF)2 and FeBd2(((C6H5)2P(S))(2-NHCH2CH2Py)-
Gm)(BF)2) contain two strongly donor centers per a clathro-
chelate molecule (sulfur atom of the diphenylthiophosphine
group and nitrogen atom of the pyridyl moiety), and they were
used as the macrobicyclic ligands toward palladium(II) ion
(Scheme 6). The resulting Pd,Fe-binuclear 1 : 1 complexes were
isolated in high yields and then tested as potent catalysts of
the Suzuki cross-coupling reaction (vide infra). The relative
stability of these complexes can be explained by the high donor
ability of the above ribbed substituents, as well as by the dis-
position of their donor centers, allowing them to form thermo-
dynamically favorable16 five- and six-membered chelate cycles.
In the case of their macrobicyclic analog FeBd2(((C6H5)2-
P(S))(CH3SCH2CH2NCH3)Gm)(BF)2, its palladium(II) complex
was detected in solution only; we failed to isolate it in the
solid state due to a fast decomposition. The potent donor
amino group of this N,P-substituted macrobicyclic complex
has a substantial amide character as a result of its conjugation
with a polyazomethine quasi-aromatic cage framework17 and,
therefore, a poor donor ability, while the two sulfur atoms
belonging to different ribbed substituents are far from each
other and cannot form a stable chelate cycle.
(((C6H5)2P(S))(2-NCH2CH2Py)Gm)(BF)2)Cl]
with
N,S-donor
macrobicyclic ligands are shown in Fig. 1–7; the main geometri-
cal parameters of the FeN6 and PdN2ClS coordination polyhedra
and those of the clathrochelate frameworks are listed in Tables
1 and 2. The average Fe–N distances in all the compounds ana-
lyzed fall within 1.905–1.915 Å, which is characteristic of low-
spin iron(II) complexes. The encapsulated iron(II) ions are situ-
The complexes obtained were characterized using elemental
analysis, MALDI-TOF mass spectrometry, IR, UV-vis, 1H, 11B,
13C{1H}, 19F{1H} and 31P{1H} NMR spectroscopies and by X-ray
diffraction.
The thiophosphorylated P,Cl- and P,N-substituted ribbed-
functionalized mono- and bis-clathrochelates FeBd2(((C6H5)2-
P(S))ClGm)(BF)2, FeBd2(((C6H5)2P(S))(n-C4H9NH)Gm)(BF)2, FeBd2-
Fig. 1 General view of clathrochelate FeBd2(((C6H5)2P(S))ClGm)(BF)2.
Hereafter, the non-hydrogen atoms are represented as thermal ellip-
soids (p = 50%).
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Fig. 2 General view of P,N-substituted ribbed-functionalized clathro-
chelate FeBd2(((C6H5)2P(S))(n-C4H9NH)Gm)(BF)2; intramolecular N–H⋯S
bond is depicted as a dashed line.
Fig. 4 General view of P,N-substituted ribbed-functionalized clathro-
chelate FeBd2(((C6H5)2P(S))(CH3SCH2CH2NCH3)Gm)(BF)2. Only one of
two disordered methyl and phenyl moieties is shown.
Fig. 5 General view of bis-clathrochelate [FeBd2(((C6H5)2P(S))Gm)-
(BF)2]2(NH(CH2)5NH) (its phenyl substituents are shown as grey balls for
clarity); intramolecular N–H⋯S bonds are shown as dashed lines.
Fig. 3 General view of P,N-substituted ribbed-functionalized clathro-
chelate FeBd2(((C6H5)2P(S))(2-NHCH2Py)Gm)(BF)2; intramolecular N–
H⋯S bond is depicted as a dashed line.
ated almost in the centres of their FeN6-coordination polyhedra,
although 0.02–0.03 Å shifted (with an exception of one complex
FeBd2(((C6H5)2P(S))(CH3SCH2CH2NCH3)Gm)(BF)2) along their
B⋯Fe⋯B C3-pseudoaxes in the direction of the N2–N4–N6 tri-
angular bases formed by two phenyl-containing donor oxime
groups and a phosphorylated moiety.
The FeN6 coordination polyhedra possess a similar dis-
torted trigonal prismatic (TP) – trigonal antiprismatic (TAP)
geometry (the distortion angle φ = 0° for a TP and φ = 60° for a
TAP). The φ values for the previously reported monoribbed-
functionalized bis-α-benzyldioximate iron(II) clathrochelates10i,j,18
vary from 21 to 24° with the heights h of these TP – TAP
polyhedra being 2.33 Å. Among the thiophosphorylated bis-
α-benzyldioximate iron(II) mono- and bis-clathrochelates
obtained, these characteristic values were observed only in the
Fig. 6 General view of the palladium(II) complex [Pd(FeBd2(((C6H5)2P(S))-
(2-NCH2Py)Gm)(BF)2)Cl] with a N,S-donor macrobicyclic ligand.
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case
of
the
monothiophosphorylated
precursor relatively rigid five- (PdN2C2) and six-membered (PdNC2PS or
FeBd2(((C6H5)2P(S))ClGm)(BF)2. The φ and h values for P,N-sub- PdN2C3) cycles are formed in the case of the complexes
stituted mono- and bis-clathrochelates and their palladium(II) [Pd(FeBd2(((C6H5)2P(S))(2-NCH2Py)Gm)(BF)2)Cl] and [Pd-
complexes vary from 25.8 to 28.6° and from 2.29 to 2.32 Å, (FeBd2(((C6H5)2P(S))(2-NCH2CH2Py)Gm)(BF)2)Cl]. In contrast,
respectively. At the same time, the bite angles α (half of the only weak intramolecular Cl⋯π interaction was found in a
chelate N–Fe–N angle) are similar for all these X-rayed bis- crystal of monothiophosphorylated precursor FeBd2(((C6H5)2-
α-benzyldioximate iron(II) clathrochelates (approximately 39°); P(S))ClGm)(BF)2; for its diphenylthiophosphoryl group the di-
so an additional TAP distortion of P,N-substituted cage com- hedral angle between the mean planes of one of the phenyl
plexes is caused by intramolecular interactions. Thus, N–H⋯S substituents and that of the Cl1–C1–C2–P1 moiety is equal to
intramolecular interactions with r(N⋯S) from 3.16(1) to 3.22(1) 67.4(3)°, and the distance from Cl1 atom to the mean plane is
Å and N–H–S angles from 139 to 152° were found in mono- approximately 3.15(1) Å. Characteristics of the clathrochelate
and
bis-clathrochelate
molecules
FeBd2(((C6H5)2P(S))- framework in FeBd2(((C6H5)2P(S))(CH3SCH2CH2NCH3)Gm)(BF)2
(n-C4H9NH)Gm)(BF)2, FeBd2(((C6H5)2P(S))(2-NHCH2Py)Gm)(BF)2 are intermediate between that of its monochloroclathrochelate
and [FeBd2(((C6H5)2P(S))Gm)(BF)2]2(NH(CH2)5NH), while the precursor and those of other P,N-substituted cage compounds.
The coordination of the thiophosphoryl groups of macro-
bicyclic ligands FeBd2(((C6H5)2P(S))(2-NHCH2Py)Gm)(BF)2 and
(FeBd2(((C6H5)2P(S))(2-NCH2CH2Py)Gm)(BF)2) to palladium(II)
ion causes the elongation of their PvS bonds from approxi-
mately 1.95 to 1.99 Å. The five-membered Pd-containing
chelate cycle in [Pd(FeBd2(((C6H5)2P(S))(2-NCH2Py)Gm)(BF)2)-
Cl] has an envelope conformation, with the donor nitrogen
atom N7 deviating by 0.70(2) Å. The six-membered PdNC2PS
and PdN2C3 chelate cycles in both the palladium complexes
[Pd(FeBd2(((C6H5)2P(S))(2-NCH2Py)Gm)(BF)2)Cl]
and
[Pd-
(FeBd2(((C6H5)2P(S))(2-NCH2CH2Py)Gm)(BF)2)Cl] have a half-
chair conformation. The palladium and sulfur atoms are
deviated by −1.03(1)/−0.89(1) and 0.41(1)/0.62(1) Å from the
mean planes of their PdNC2PS cycles, while in the case of
PdN2C3 cycles the N7 and C31 atoms are deviated by −0.69(1)
and 0.18(1) Å, respectively. In both these complexes, the palla-
dium(II) ion has a twisted square-planar N2SCl-coordination
environment with the dihedral angles between their Pd1–N7–
N8 and Pd1–Cl1–S1 planes of approximately 8.9(4) and 6.9(3)°,
respectively.
Fig. 7 General view of the palladium(II) complex [Pd(FeBd2(((C6H5)2P(S))-
(2-NCH2CH2Py)Gm)(BF)2)Cl] with a N,S-donor macrobicyclic ligand.
Table 1 Main geometrical parameters of the monothiophosphorylated iron(II) clathrochelate precursor and its P,N-substituted bis-macrobicyclic
derivative
FeBd2(((C6H5)2P(S))ClGm)(BF)2
Fe2+
[FeBd2(((C6H5)2P(S))Gm)(BF)2]2 (NH(CH2)5NH)
Parameter
Metal ion
Fe2+(1)
Fe2+(2)
M–N (Å)
1.897(3)–1.925(3)
av. 1.915
1.902(4)–1.916(4)
av. 1.909
1.893(4)–1.932(4)
av. 1.907
Fe1⋯B1 (Å)
Fe1⋯B2 (Å)
N–O (Å)
2.993(5)
2.978(5)
1.349(4)–1.379(4)
av. 1.369
2.960(7)
2.987(7)
1.373(5)–1.417(5)
av. 1.386
2.957(7)
2.958(7)
1.343(5)–1.394(5)
av. 1.373
B–O (Å)
CvN (Å)
C–C (Å)
1.471(4)–1.490(5)
av. 1.484
1.302(5)–1.328(5)
av. 1.313
1.449(6)–1.457(6)
av. 1.454
1.464(7)–1.515(7)
av. 1.485
1.288(6)–1.348(7)
av. 1.316
1.449(7)–1.498(7)
av. 1.463
1.476(7)–1.499(7)
av. 1.487
1.306(7)–1.345(7)
av. 1.324
1.437(7)–1.481(8)
av. 1.455
PvS (Å)
NvC–CvN (°)
1.946(2)
8.0(7)–12.1(7)
av. 9.6
1.933(3)
6.2(5)–9.0(5)
av. 7.9
1.953(2)
8.1(5)–14.8(5)
av. 11.6
φ (°)
α (°)
h (Å)
24.0
39.2
2.34
26.0
39.0
2.30
28.6
39.2
2.29
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1
The number and position of the signals in the solution H,
11B{1H}, 19F{1H}, 13C{1H} and 31P{1H} NMR spectra of the dia-
magnetic monoribbed-functionalized iron(II) complexes syn-
thesized as well as the ratios of the integral intensities of
protons of their chelate α-benzyldioximate fragments and
those of the ribbed P- and N-substituents in the 1H NMR
spectra confirmed the composition and symmetry of these
thiophosphorylated and P,N-substituted mono- and bis-
clathrochelates as well as their complexes as N,S-donor macro-
bicyclic ligands with palladium(II) ion. In their 13C{1H} NMR
spectra, the signals of four types of the azomethine carbon
atoms are observed indicating the absence of a symmetry
plane that passes through the middles of the chelate C–C
bonds in the α-dioximate fragments and the encapsulated iron(II)
ion. The 11B{1H} and 19F{1H} NMR spectra also suggest
non-equivalence of their tetrahedral O3BF capping fragments.
In the case of N,S-donor clathrochelate ligand FeBd2(((C6H5)2-
P(S))(2-NHCH2Py)Gm)(BF)2 with a methylene bridging frag-
ment, its coordination to the palladium(II) ion, followed by the
deprotonation of the amino group and the formation of a five-
membered PdN2C2 chelate cycle, resulted in the substantial
(up to 12 ppm) shifts of the 13C NMR signals of these carbon
atoms. The same effect of the coordination to Pd2+ ion is
observed for the diphenylphosphine sulfide donor group in
the 31P{1H} NMR spectrum of this complex.
In contrast, for the macrobicyclic ligand FeBd2(((C6H5)2P(S))-
(2-NHCH2CH2Py)Gm)(BF)2 with an ethylene spacer fragment
forming a six-membered PdN2C3 cyclic moiety, the changes in
the 13C{1H} NMR spectrum after its coordination to this ion
are small, whereas the 31P{1H} NMR signal of its thiophos-
phoryl donor group undergoes almost the same shift (approxi-
mately 3.5 ppm) as in the case of the methylene-bridged
complex FeBd2(((C6H5)2P(S))(2-NHCH2Py)Gm)(BF)2.
While the deconvoluted solution UV-vis spectrum of the
iron(II) dichloroclathrochelate precursor contains three inten-
sive bands in the visible region from 400 to 470 nm assigned
to the metal-to-ligand Fed→Lπ* charge transfer (MLCT) bands
in the highly π-conjugated polyazomethine macrobicyclic
framework, two new bands at 500 and 515 nm appear in the
spectrum
of
its
monothiophosphorylated
derivative
FeBd2(((C6H5)2P(S))ClGm)(BF)2 (see ESI, Table S3¶). The latter
may be caused by the electron-donating diphenylphosphine
sulfide substituent in its ribbed chelate fragment. Further
functionalization of this monochloroclathrochelate precursor
with the electron-donating amine substituents leads to a sub-
stantial (by approximately 20–30 nm) longwave-shift of the
band at 515 nm. The coordination of clathrochelates
FeBd2(((C6H5)2P(S))(2-NHCH2CH2Py)Gm)(BF)2 and
FeBd2-
(((C6H5)2P(S))(2-NHCH2Py)Gm)(BF)2 to the palladium(II) ion
led to the additional longwave-shift of this band by 10 and
40 nm and the appearance of a new band at 577 and 605 nm,
respectively. These facts are indicative of a dramatic redistribu-
tion of the electron density in the π-conjugated clathrochelate
framework caused by its ribbed functionalization with
diphenylphosphine sulfide and amine substituents as well as
by their further coordination to the palladium ion.
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Conclusions
We successfully performed the phosphorylation of a cage
metal complex giving the first monophosphorylated iron(II)
clathrochelate. This complex undergoes further nucleophilic
substitution with aliphatic mono- and diamines, leading to
P,N-substituted mono- and bis-clathrochelates. Those with the
donor diphenylthiophosphine and pyridyl groups form Pd,Fe-
binuclear 1 : 1 complexes, which were found to be efficient and
structure-dependent catalysts of the Suzuki cross-coupling
reaction.
Scheme 7 Suzuki cross-coupling reaction in the presence of the Pd,
Fe-binuclear complexes.
Table 3 Yields of Suzuki cross-coupling reactions catalyzed by the Experimental section
palladium(II) complexes with N,S-donor clathrochelate ligands
General considerations
Catalyst
Substrate
C6H5I
Conversion (%)
The reagents used, FeCl2·4H2O, α-benzyldioxime (denoted as
H2Bd), BF3·O(C2H5)2, diphenylphosphine sulfide, triethylben-
zylammonium chloride, n-butylamine, 2-aminomethyl-
[Pd(FeBd2(((C6H5)2P(S))-
(2-NCH2CH2Py)Gm)(BF)2)Cl]
[Pd(FeBd2(((C6H5)2P(S))-
(2-NCH2Py)Gm)(BF)2)Cl]
[Pd(FeBd2(((C6H5)2P(S))-
(2-NCH2CH2Py)Gm)(BF)2)Cl]
[Pd(FeBd2(((C6H5)2P(S))-
(2-NCH2Py)Gm)(BF)2)Cl]
>99
98
C6H5I
pyridine,
2-aminoethylpyridine,
N-methyl-2-(methylthio)-
ethylamine, cadaverine, complex Pd(C6H5CN)2Cl2, triethyl-
amine, sorbents, acids, bases, and organic solvents were
obtained commercially (SAF). The dichloroglyoxime (denoted
as Cl2GmH2) was prepared by chlorination of glyoxime as
described in ref. 19. The dichloroclathrochelate precursor
FeBd2(Cl2Gm)(BF)2 was obtained as described elsewhere.10b
Analytical data (C, H, N content) were obtained with a Carlo
Erba model 1106 microanalyzer. The iron and phosphorus
content were determined spectrophotometrically. The sulfur
content was determined by titrimetry, using the Shoeniger
method.
MALDI-TOF mass spectra were recorded in both the positive
and the negative spectral regions using a MALDI-TOF-MS
Bruker Autoflex mass spectrometer in the reflecto-mol mode.
The ionization was induced by a UV-laser with a wavelength of
336 nm. The sample was applied to a nickel plate, and
2,5-dihydroxybenzoic acid was used as a matrix. The accuracy
of the measurements was 0.1%.
C6H5Br
C6H5Br
78
71
The maxima in the spectra of the monoclathrochelate
FeBd2(((C6H5)2P(S))(H2N(CH2)5NH)Gm)(BF)2 with the terminal
amino
group
and
its
bis-clathrochelate
derivative
[FeBd2(((C6H5)2P(S))Gm)(BF)2]2(NH(CH2)5NH) are very similar,
suggesting the absence of electronic interactions between the
FeN6 chromophores in this ditopic molecule with a labile alkyl
spacer. At the same time, the intensities of its MLCT bands are
approximately two times higher than those for the initial
monoclathrochelate, due to the presence of two such chromo-
phores per bis-clathrochelate molecule of [FeBd2(((C6H5)2P(S))-
Gm)(BF)2]2(NH(CH2)5NH). The spectra of all these clathroche-
lates also contain intensive bands in the UV region, assigned
to the π,π*-transitions both in the π-conjugated α-dioximate
chelate fragments of their macrobicyclic ligands and in the
functionalizing ribbed substituents.
IR spectra of the solid sample (KBr tablets) in the range
400–4000 cm−1 were recorded with a Nicolet Magna-IR 750
FTIR-spectrophotometer.
The palladium(II) complexes [Pd(FeBd2(((C6H5)2P(S))-
UV-vis spectra of the solutions in dichloromethane were
recorded in the range 230–800 nm with a Lambda 9 Perkin
Elmer spectrophotometer. The individual Gaussian com-
ponents of these spectra were calculated using the SPECTRA
program.
(2-NCH2CH2Py)Gm)(BF)2)Cl]
and
[Pd(FeBd2(((C6H5)2P(S))-
(2-NCH2Py)Gm)(BF)2)Cl] were studied as potent catalysts of the
model Suzuki cross-coupling reaction of iodobenzene with
phenylboronic acid in a DMF solution at 100 °C for 4 h using
K3PO4 as an inorganic base (Scheme 7).
1H, 11B{1H}, 19F{1H}, 13C{1H} and 31P{1H} NMR spectra of
the complexes obtained were recorded from their CD2Cl2 solu-
tions using a Bruker Avance 400 spectrometer.
In both cases, very high conversion of iodobenzene to
biphenyl was observed (Table 3). To further evaluate their cata-
lytic activity, a less reactive bromobenzene was used as a sub-
strate. As it can be seen from Table 3, the palladium(II)
complex of clathrochelate ligand FeBd2(((C6H5)2P(S))-
(2-NCH2CH2Py)Gm)(BF)2, with the ethylene spacer fragment
forming a six-membered PdN2C3 chelate cycle showed a better
conversion in this system as compared with its methylene-con-
taining analog FeBd2(((C6H5)2P(S))(2-NCH2Py)Gm)(BF)2 giving
the five-membered PdN2C2 cyclic moiety.
Synthesis
FeBd2(((C6H5)2P(S))ClGm)(BF)2. Complex
FeBd2(Cl2Gm)-
(BF)2 (1 g, 1.34 mmol), diphenylphosphine sulfide (0.345 g,
1.58 mmol), and triethylbenzylammonium chloride (0.018 g,
5 mol%) were dissolved in dichloromethane (10 ml) and 50%
NaOH aqueous solution (0.45 g) was added dropwise to the
9684 | Dalton Trans., 2014, 43, 9677–9689
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vigorously stirring reaction mixture. The reaction mixture was (CH2Cl2): λmax, nm (ε × 10−3, mol−1 L cm−1): 256(23), 283(15),
stirred for 1.5 h, then diluted with dichloromethane (30 ml) 300(11), 356(3.4), 414(3.9), 465(8.2), 496(20), 542(6.6).
and washed with water (30 ml, in two portions). The dichloro-
FeBd2(((C6H5)2P(S))(2-NHCH2Py)Gm)(BF)2. Complex
methane solution was evaporated to dryness and purified by FeBd2(((C6H5)2P(S))ClGm)(BF)2 (0.1 g, 0.108 mmol) was dis-
preparative TLC on silica gel (the gradient eluents: hexane– solved/suspended in acetonitrile (2 ml) and 2-aminomethyl-
dichloromethane 1 : 1–1 : 4 mixtures). The major elute was pyridine (0.014 g, 0.129 mmol) and triethylamine (0.018 ml,
evaporated to dryness, washed with hexane and dried in vacuo. 0.129 mmol) were added. The reaction mixture was stirred for
Yield: 1.075 g (86%). Anal. Calc. for C42H30N6O6B2ClF2FePS 12 h and evaporated to dryness. The solid residue was washed
(%): C, 54.32; H, 3.26; N, 9.05; S, 3.45. Found (%): C, 54.19; H, with water (5 ml) and extracted with dichloromethane (10 ml,
3.29; N, 8.95; S, 3.32. MS (MALDI-TOF) m/z (I, %): (positive in two portions). The dichloromethane solution was evapo-
range) 929 (100) [M]+•, 952 (15) [M + Na+]+, 968 (5) [M + K+]+; rated to dryness and purified by preparative TLC on silica
1
(negative range) −929 [M]−•. H NMR (CD2Cl2): δ, ppm; J, Hz: gel (the gradual eluents: dichloromethane–hexane 1 : 1–10 :
7.15–7.30 (m, 20H, Ph(Bd)), 7.35–7.45 (m, 4H, meta-H (PhP)), 1 mixtures). The major elute was evaporated to dryness,
7.45–7.55 (m, 2H, para-H (PhP)), 7.85 (dd, 4H, ortho-H (Ph-P), washed with hexane and dried in vacuo. Yield: 0.093 g (88%).
3J
1
1
= 7.8, 3J
1
31 = 14.6). 13C{1H} NMR (CD2Cl2) δ, ppm; J, Hz: Anal. Calc. for C48H37N8O6B2F2FePS (%): C, 57.63; H, 3.73; N,
H–
H
H–
P
128.67 (s, ortho-Ph(Bd)), 129.37 (s, ipso-Ph(Bd)), 129.31 (s, 11.20; S, 3.21. Found (%): C, 57.52; H, 3.84; N, 11.17; S, 2.98.
ClCvN), 129.32 (d, 3J13 31 = 13.6, meta-PhP), 131.11 (s, para-Ph- MS (MALDI-TOF) m/z (I, %): 1000 (80) [M]+•, 1023 (90)
C–
P
1
(Bd)), 131.17 (s, meta-Ph(Bd)), 131.27 (d, JPC = 91.3, ipso-C in [M + Na+]+, 1039 (100) [M + K+]+. 1H NMR (CD2Cl2): δ, ppm;
3
C6H5P), 132.09 (d, 2JPC = 11.4, ortho-C6H5P), 132.96 (d, 4J13 31
=
J, Hz: 5.11 (d, 2H, CH2NH, J
1
1
= 5.8), 7.15 (dd, 1H, C3H(Py),
C–
P
H–
H
3.0, para-PhP), 151.71 (d, 1J13 31 = 69.42, PCvN), 159.36, 3J
1
1
= 7.2, 4J
1
1
= 2.0), 7.25–7.45 (m, 20H + 1H, Ph(Bd) + C5H
C–
P
H–
H
H–
H
159.81 (both s, PhCvN). 31P{1H} NMR (CD2Cl2) δ, ppm: 32.01. (Py)), 7.46–7.65 (m, 6H + 1H, meta- + para-PhP + C4H(Py)), 7.91
19F{1H} NMR (CD2Cl2) δ, ppm; J, Hz: −168.40, −169.30 (both q, (dd, 4H, ortho-PhP, J
1
1
= 7.5, J
= 4.5), 9.04 (m, 1H, NH, J
31 = 15.0), 8.47 (d, 1H, C6H
3
3
1
H–
H
H–
P
3
1J11 19 = 16.0). 11B{1H} NMR (CD2Cl2) δ, ppm; J, Hz: 3.25, 3.71 (Py), J
1
1
1
1
= 5.8). 13C{1H} NMR
3
B–
F
H–
H
H–
H
(both d, 1J11 19 = 16.0). IR (KBr) ν/cm−1: 920, 931, 943, 1067, (CD2Cl2) δ, ppm; J, Hz: 50.59 (s, CH2NH), 121.82 (s, C3(Py)),
B–
F
1108, 1158 ν(N–O), 1220 m ν(B–O) + ν(B–F), 1549, 1580 ν(CvN). 121.95 (s, C5(Py)), 127.71, 127.81 (both s, ortho-Ph(Bd)), 128.50
UV-vis (CH2Cl2): λmax, nm (ε × 10−3, mol−1 L cm−1): 262(33), (d, 3J13 31 = 13.9, meta-PhP), 128.86, 129.17 (both s, ipso-Ph
C–
P
299(11), 355(4.0), 412(4.4), 441(7.7), 467(19), 499(15), 514(2.9).
FeBd2(((C6H5)2P(S))(n-C4H9NH)Gm)(BF)2. Complex FeBd2- (Bd)), 130.78 (d, 1J13 31 = 91.3, ipso-PhP), 131.70 (d, 2J13 31
=
P
(Bd)), 129.84 (s, para-Ph(Bd)), 130.40, 130.76 (both s, meta-Ph
C–
P
C–
4
(((C6H5)2P(S))ClGm)(BF)2 (0.1 g, 0.108 mmol) was dissolved/ 12.1, ortho-PhP), 132.28 (d, J13 31 = 3.3, para-PhP), 136.32 (s,
C–
P
suspended in acetonitrile (2 ml) and n-butylamine (0.2 g, C4(Py)), 141.83 (d, 1J13 31 = 63.9, PCvN), 148.76 (s, C6(Py)),
C–
P
2.74 mmol) was added to the stirred solution. The reaction 151.91 (br. s, NHCvN), 155.75 (s, PhCvN), 157.19 (s, C2(Py)),
mixture was stirred for 12 h and left overnight. The precipitate 157.56 (s, PhCvN). 31P{1H} NMR (CD2Cl2) δ, ppm: 34.79.
formed was filtered off, washed with acetonitrile (1 ml) and 19F{1H} NMR (CD2Cl2) δ, ppm; J, Hz: −166.30, −166.80 (both q,
dichloromethane (1 ml), and dried in vacuo. Yield: 0.099 g 1J11 19 = 15.0). 11B{1H} NMR (CD2Cl2) δ, ppm; J, Hz: 3.43, 3.69
B–
F
(95%). Anal. Calc. for C46H40N7O6B2F2FePS (%): C, 57.23; H, (both d, 1J11 19 = 15.0). IR (KBr) ν/cm−1: 943 m, 1061, 1110, 1175
B–
F
4.18; N, 10.16. Found (%): C, 57.32; H, 4.24; N, 10.28. MS ν(N–O), 1211 m ν(B–O) + ν(B–F), 1568 ν(CvN), 1591 m ν(CvN)
(MALDI-TOF) m/z (I, %): 965 (100) [M]+•, 988 (10) [M + Na+]+, + δ(N–H). UV-vis (CH2Cl2): λmax, nm (ε × 10−3, mol−1 L cm−1):
1
1004 (15) [M + K+]+. H NMR (CD2Cl2): δ, ppm; J, Hz: 0.86 (m, 256(18), 284(16), 320(3.3), 407(3.1), 469(5.0), 496(12), 533(4.3).
3
3
1
3H, CH3, J
1
1
= 7.3), 1.29 (sextet, 2H, CH2CH3, J = 7.6),
1
FeBd2(((C6H5)2P(S))(2-NHCH2CH2Py)Gm)(BF)2. This complex
= 7.4), 3.78 (q, 2H, was obtained like the previous one except that 2-aminoethyl-
H
H–
H
H– H
1.49 (pentet, 2H, CH2CH2CH3, 3J
1
1
H–
CH2NH, 3J
1
1
= 7.4), 7.22–7.42 (m, 20H, Ph(Bd)), 7.45–7.60 (m, pyridine (0.016 g, 0.130 mmol) was used instead of 2-amino-
H–
H
6H, meta- + para-PhP), 7.88 (dd, 4H, ortho-PhP, 3J
1
1
= 7.4, methylpyridine. The product obtained was purified by
H
H–
3J
1
31 = 14.8), 8.36 (m, 1H, NH, 3J
1
1
= 5.3). 13C{1H} NMR preparative TLC on silica gel (eluent: dichloromethane–aceto-
H–
P
H–
H
(CD2Cl2) δ, ppm; J, Hz: 13.71 (s, CH3), 19.80 (s, CH2CH3), 32.58 nitrile 10 : 1 mixture). The major elute was evaporated to
(s, CH2CH2CH3), 45.79 (s, CH2NH), 127.73, 127.82 (both s, dryness, washed with hexane and dried in vacuo. Yield: 0.061 g
ortho-Ph(Bd)), 128.62 (d, 3J13 31 = 13.9, meta-PhP), 128.87, (56%). Anal. Calc. for C49H39N8O6B2F2FePS (%): C, 58.02; H,
C–
P
129.19 (both s, ipso-Ph(Bd)), 129.84 (s, para-Ph(Bd)), 130.40 (s, 3.88; N, 11.05; P, 3.05; S, 3.16. Found (%): C, 57.97; H, 3.78; N,
meta-Ph(Bd)), 130.68 (d, 1J13 31 = 91.3, ipso-PhP), 130.78 (s, 10.90; P, 2.98; S, 3.09. MS (MALDI-TOF) m/z (I, %): 1014 (100)
C–
P
meta-Ph(Bd)), 131.63 (d, 2J13 31 = 12.1, ortho-PhP), 132.44 (d, [M]+•, 1037 (60) [M + Na+]+, 1053 (40) [M + K+]+. 1H NMR
C–
P
3
4J13 31 = 3.3, para-PhP), 142.33 (d, 1J13 31 = 64.9, PCvN), (CD2Cl2): δ, ppm; J, Hz: 3.14 (m, 2H, CH2Py, J
1
1
= 6.6), 4.14
C–
P
C–
P
H–
H
151.94 (d, 2J13 31 = 16.9, NHCvN), 155.72, 157.68 (both s, (q, 2H, CH2NH, 3J = 6.6), 7.12 (m, 1H, C3H(Py), 3J
1
1
1
1
= 5.1),
H
C–
P
H–
H
H–
PhCvN). 31P{1H} NMR (CD2Cl2) δ, ppm: 34.68. 19F{1H} NMR 7.20–7.45 (m, 20H + 1H, Ph(Bd) + C5H(Py)), 7.46–7.65 (m, 6H +
(CD2Cl2) δ, ppm; J, Hz: −167.50, −169.04 (both q, 1J11 19
=
1H, meta- + para-PhP + C4H(Py)), 7.88 (dd, 4H, ortho-PhP,
B–
F
12.0). 11B{1H} NMR (CD2Cl2) δ, ppm; J, Hz: 3.41, 3.74 (both d, 3J
1
1
= 7.5, 3J
1
31 = 14.8), 8.52 (d, 1H, C6H(Py), 3J
1
1
= 3.6),
H–
H
H–
H–
H
P3
1J11 19 = 12.0). IR (KBr) ν/cm−1: 911, 941, 1060, 1109, 1176 8.68 (m, 1H, NH, J
1
1
= 6.6). 13C{1H} NMR (CD2Cl2) δ, ppm;
B–
F
H–
H
ν(N–O), 1210 m ν(B–O) + ν(B–F), 1547, 1581 ν(CvN). UV-vis J, Hz: 39.65 (s, CH2Py), 45.21 (s, CH2NH), 121.29 (s, C3(Py)),
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123.59 (s, C5(Py)), 127.70, 127.77 (both s, ortho-Ph(Bd)), 128.54 rated to dryness. The solid residue was washed with water
(d, 3J13 31 = 13.9, meta-PhP), 128.84, 129.16 (both s, ipso-Ph (5 ml) and extracted with dichloromethane (10 ml, in two por-
C–
P
(Bd)), 129.80 (s, para-Ph(Bd)), 130.36 (s, meta-Ph(Bd)), 130.65 tions). The dichloromethane solution was evaporated to
1
(d, J13 31 = 91.7, ipso-PhP), 130.75 (s, meta-Ph(Bd)), 131.57 (d, dryness and purified by preparative TLC on silica gel (first
C–
P
2J13 31 = 12.1, ortho-PhP), 132.33 (d, 4J13 31 = 3.3, para-PhP), eluent: dichloromethane–acetonitrile 1 : 1 mixture, second
C–
P
C–
P
1
136.30 (s, C4(Py)), 142.39 (d, J13 31 = 63.8, PCvN), 149.09 (s, eluent: acetonitrile). The second elute was evaporated to
C–
P
C6(Py)), 151.76 (d, 2J13 31 = 18.0, NHCvN), 155.70, 157.66 dryness, washed with hexane and dried in vacuo. Yield: 0.097 g
C–
P
(both s, PhCvN), 158.66 (s, C2(Py)). 31P{1H} NMR (CD2Cl2) δ, (90%). Anal. Calc. for C47H43N8O6B2F2FePS (%): C, 56.77; H,
ppm: 34.63. 19F{1H} NMR (CD2Cl2) δ, ppm; J, Hz: −108.65, 4.36; N, 11.27. Found (%): C, 56.60; H, 4.55; N, 11.30. MS
1
−110.24 (both q, J11 19 = 15.0). 11B{1H} NMR (CD2Cl2) δ, ppm; (MALDI-TOF) m/z (I, %): 994 (90) [M]+•, 1017 (60) [M + Na+]+,
B–
F
1
J, Hz: 3.31, 3.46 (both d, J11 19 = 15.0). IR (KBr) ν/cm−1: 903, 1033 (100) [M + K+]+. 1H NMR (CD2Cl2): δ, ppm; J, Hz: 1.34,
B–
F
910, 922, 941, 950, 1058, 1111, 1159, 1173 ν(N–O), 1209 m ν(B– 1.45, 1.53 (all br. s, 6H, CH2CH2CH2), 2.42 (br. s, 2H, NH2),
O) + ν(B–F), 1544 m ν(CvN) + δ(N–H), 1578 ν(CvN). UV-vis 2.66 (br. s, 2H, CH2NH2), 3.76 (q, 2H, CH2NH, 3J
= 5.8),
1
1
H–
H
(CH2Cl2): λmax, nm (ε × 10−3, mol−1 L cm−1): 250(14), 267(3.6), 7.22–7.50 (m, 20H, Ph(Bd)), 7.50–7.70 (m, 6H, meta- + para-
3
3
1
277(20), 299(4.8), 406(2.7), 490(20), 543(4.6).
FeBd2(((C6H5)2P(S))(CH3SCH2CH2NCH3)Gm)(BF)2. Complex
PhP), 7.92 (dd, 4H, ortho-PhP, J
1
1
= 7.1, J 31 = 14.5), 8.38
H–
H H– P
3
(m, 1H, NH, J
1
1
= 6.0). 13C{1H} NMR (CD2Cl2) δ, ppm; J, Hz:
H–
H
FeBd2(((C6H5)2P(S))ClGm)(BF)2 (0.1 g, 0.108 mmol) was dis- 23.79, 30.31, 32.42 (all s, CH2CH2CH2), 41.51 (s, CH2NH2),
solved/suspended in acetonitrile (3 ml) and N-methyl- 45.91 (s, CH2NH), 127.89, 127.94 (both s, ortho-Ph(Bd)), 128.65
2-(methylthio)ethylamine (0.012 g, 0.110 mmol) and triethyl- (d, 3J13 31 = 13.9, meta-PhP), 128.97, 129.20 (both s, ipso-Ph-
C–
P
amine (0.015 ml, 0.110 mmol) were added. The reaction (Bd)), 130.03 (s, para-Ph(Bd)), 130.25, 130.54 (both s, meta-Ph-
mixture was stirred for 12 h and evaporated to dryness. The (Bd)), 130.71 (d, 1J13 31 = 91.7, ipso-PhP), 131.58 (d, 2J13 31
=
P
C–
P
C–
4
solid residue was washed with water (5 ml) and extracted with 12.1, ortho-PhP), 132.52 (d, J13 31 = 2.9, para-PhP), 143.04 (d,
C–
P
dichloromethane (10 ml, in two portions). The dichloro- 1J13 31 = 64.9, PCvN), 152.05 (d, 2J13 31 = 16.1, NCvN), 155.94,
C–
P
C–
P
methane extract was evaporated to dryness and purified by pre- 157.93 (both s, PhCvN). 31P{1H} NMR (CD2Cl2) δ, ppm: 34.74.
parative TLC on silica gel (eluent: dichloromethane–hexane 19F{1H} NMR (CD2Cl2) δ, ppm; J, Hz: −167.40, −168.90 (both q,
1 : 1 mixture). The major elute was evaporated to dryness, 1J11 19 = 11.0). 11B{1H} NMR (CD2Cl2) δ, ppm; J, Hz: 3.40, 3.70
B–
F
washed with hexane and dried in vacuo. Yield: 0.094 g (87%). (both d, J11 19 = 11.0). IR (KBr) ν/cm−1: 922, 944, 1067, 1110,
1
B–
F
Anal. Calc. for C46H40N7O6B2F2FePS2 (%): C, 55.39; H, 4.04; N, 1176 ν(N–O), 1211 m ν(B–O) + ν(B–F), 1543, 1580sh ν(CvN),
9.83. Found (%): C, 55.30; H, 3.90; N, 9.69. MS (MALDI-TOF) 1604 δ(N–H). UV-vis (CH2Cl2): λmax, nm (ε × 10−3, mol−1
L
m/z (I, %): (positive range) 625 (100) [M–((Ph2PS)(MeS- cm−1): 256(24), 289(17), 320(5.1), 378(3.4), 429(3.6), 468(6.3),
(CH2)2NMe)Gm–O)]+•, 740 (40) [M–Ph2PS–2 Me]+•; (negative 496(16), 533(6.9).
range) – 676 (100) [M–Ph2PS–MeS(CH2)2NMe]−•, −840 (25)
[M + DHB–Ph2PS–MeS(CH2)2NMe]−• 1H NMR (CD2Cl2): δ,
ppm; J, Hz: 2.12 (s, 3H, CH3S), 2.78 (s, 3H, CH3N), 2.66 (m, 2H,
[FeBd2(((C6H5)2P(S))Gm)(BF)2]2(NH(CH2)5NH)
Procedure 1. Complex FeBd2{((C6H5)2P(S))ClGm}(BF)2 (0.2 g,
0.216 mmol) was dissolved/suspended in acetonitrile (5 ml)
and cadaverine (0.006 g, 0.058 mmol) and triethylamine
(0.016 ml, 0.117 mmol) were added. The reaction mixture was
stirred for 24 h and evaporated to dryness. The solid residue
was washed with water (5 ml) and extracted with dichloro-
methane (10 ml, in two portions). The dichloromethane
extract was evaporated to dryness and purified by preparative
TLC on silica gel (eluent: dichloromethane–acetonitrile
1 : 1 mixture). The major elute was evaporated to dryness,
washed with hexane and dried in vacuo. Yield: 0.095 g (86%).
Procedure 2. Complex FeBd2(((C6H5)2P(S))(H2N(CH2)5NH)-
Gm)(BF)2 (0.05 g, 0.05 mmol) and triethylamine (0.011 ml,
0.076 mmol) were dissolved/suspended in acetonitrile (2 ml)
and complex FeBd2(((C6H5)2P(S))ClGm)(BF)2 (0.07 g,
0.076 mmol) was added. The reaction mixture was stirred for
24 h and evaporated to dryness. The solid clathrochelate
product was isolated like in Procedure 1. Yield: 0.085 g (90%).
Anal. Calc. for C89H72N14O12B4F4Fe2P2S2 (%): C, 56.66; H, 3.85;
N, 10.39. Found (%): C, 56.78; H, 4.04; N, 10.45. MS (MALDI-
TOF) m/z (I, %): 1888 (50) [M]+ •, 1911 (75) [M + Na+]+, 1927
.
3
CH2S, J
1
1
= 6.6), 3.15 (br. s, 2H, CH2N), 7.35–7.50 (m, 20H,
H–
H
Ph(Bd)), 7.58–7.68 (m, 6H, meta- + para-PhP), 8.09 (dd, 4H,
3
3
1
ortho-PhP, J
1
1
= 7.6, J
31 = 15.0). 13C{1H} NMR (CD2Cl2) δ,
H–
H
H–
P
ppm; J, Hz: 15.27 (s, SCH3), 32.33 (s, CH2S), 39.21 (s, NCH3),
55.30 (s, CH2N), 127.90 (s, ortho-Ph(Bd)), 128.36 (d, 3J13 31
=
C–
P
13.2, meta-PhP), 129.03, 129.13 (both s, ipso-Ph(Bd)), 130.12 (s,
para-Ph(Bd)), 130.35, 130.56 (both s, meta-Ph(Bd)), 130.46 (d,
1J13 31 = 91.6, ipso-PhP), 130.90 (d, 2J13 31 = 11.0, ortho-PhP),
C–
P
C–
P
131.76 (d, 4J13 31 = 2.9, para-PhP), 150.22 (d, 1J13 31 = 68.2,
C–
P
C–
P
PCvN), 151.64 (br. S, NCvN), 156.38, 158.31 (both s,
PhCvN). 31P{1H} NMR (CD2Cl2) δ, ppm: 30.59. 19F{1H} NMR
(CD2Cl2) δ, ppm; J, Hz: −167.70, −169.50 (both q, 1J11 19
=
B–
F
16.8). 11B{1H} NMR (CD2Cl2) δ, ppm; J, Hz: 3.35, 3.78 (both d,
1J11 19 = 16.8). IR (KBr) ν/cm−1: 928, 943, 1063, 1108, 1158 ν(N–
B–
F
O), 1213 m ν(B–O) + ν(B–F), 1550sh, 1580 ν(CvN). UV-vis
(CH2Cl2): λmax, nm (ε × 10−3, mol−1 L cm−1): 255(28), 267(0.9),
289(17), 290(2.4), 341(4.2), 394(1.0), 482(10), 489(13), 522(2.2).
FeBd2(((C6H5)2P(S))(H2N(CH2)5NH)Gm)(BF)2. Complex
FeBd2(((C6H5)2P(S))ClGm)(BF)2 (0.1 g, 0.108 mmol) was dis-
solved/suspended in acetonitrile (2 ml) and cadaverine (0.11 g,
1.08 mmol) and triethylamine (0.15 ml, 1.08 mmol) were
added. The reaction mixture was stirred for 12 h and evapo-
1
(100) [M + K+]+. H NMR (CD2Cl2): δ, ppm; J, Hz: 1.30 (pentet,
4H, CH2CH2CH2CH2NH, 3J
1
1
=
8.0), 1.45 (pentet, 2H,
H–
H
CH2CH2CH2NH, 3J
1
1
= 8.0), 3.73 (q, 4H, CH2NH, 3J
1
1
= 5.8),
H–
H
H– H
9686 | Dalton Trans., 2014, 43, 9677–9689
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Paper
7.25–7.35 (m, 40H, Ph(Bd)), 7.40–7.55 (m, 12H, meta- + para-
[Pd(FeBd2(((C6H5)2P(S))(2-NCH2CH2Py)Gm)(BF)2)Cl]. This
3
3
1
PhP), 7.87 (dd, 8H, ortho-PhP, J
1
1
= 8.0, J
31 = 16.0), 8.36 compound was prepared by the same procedure as the
H–
H
H–
P
3
(m, 2H, NH, J
1
1
= 5.2). 13C{1H} NMR (CD2Cl2) δ, ppm; J, Hz: complex [Pd(FeBd2{((C6H5)2P(S))[2-NCH2Py]Gm}(BF)2)Cl]; Pd-
H–
H
23.63 (s, CH2CH2CH2NH), 30.00 (s, H2CH2CH2CH2NH), 45.79 (C6H5CN)2Cl2 (0.0465 g, 0.121 mmol) and the complex
(s, CH2NH), 127.71, 127.78 (both s, ortho-Ph(Bd)), 128.66 (d, FeBd2{((C6H5)2P(S))[2-NHCH2CH2Py]Gm}(BF)2 (0.123 g,
3J13 31 = 13.9, meta-PhP), 128.92, 129.21 (both s, ipso-Ph(Bd)), 0.121 mmol) (instead of FeBd2{((C6H5)2P(S))[2-NHCH2Py]Gm}-
C–
P
129.79 (s, para-Ph(Bd)), 130.45, (s, meta-Ph(Bd)), 130.53 (d, (BF)2) were used. Yield: 0.192 g (85%). Anal. Calc. for
1J13 31 = 91.3, ipso-PhP), 130.83 (s, meta-Ph(Bd)), 131.64 (d, C49H38N8O6B2ClF2FePPdS (%): C, 50.95; H, 3.32; N, 9.70; S,
C–
P
2J13 31 = 12.1, ortho-PhP), 132.50 (d, 4J13 31 = 2.9, para-PhP), 2.78. Found (%): C, 51.10; H, 3.41; N, 9.55; S, 2.63. MS
C–
P
C–
P
142.68 (d, 1J13 31 = 64.2, PCvN), 151.71 (d, 2J13 31 = 16.9, (MALDI-TOF) m/z (I, %): (positive range) 1119 (100) [M – Cl−]+•,
C–
P
C–
P
NCvN), 155.78, 157.72 (both s, PhCvN). 31P{1H} NMR 1155 (40) [M]+•; (negative range) – 1155 [M]−•
.
1H NMR
= 6.4), 3.79
H
3
(CD2Cl2) δ, ppm: 34.67. 19F{1H} NMR (CD2Cl2) δ, ppm; J, Hz: (CD2Cl2): δ, ppm; J, Hz: 3.52 (m, 2H, CH2Py, J
1
1
H–
3
−168.30, −169.20 (both q, 1J11 19 = 12.0). 11B{1H} NMR (m, 2H, CH2NH, J
1
1
= 6.4), 7.25–7.44 (m, 20H, Ph(Bd)), 7.54
B–
F
H–
H
3
(CD2Cl2) δ, ppm; J, Hz: 3.53, 3.77 (both d, 1J11 19 = 12.0). IR (m, 1H, C4H(Py), J
1
1
= 7.8), 7.64–7.83 (m, 6H + 1H, meta- +
B–
F
H–
H
(KBr) ν/cm−1: 911, 924, 941, 1060, 1111, 1176 ν(N–O), 1212 m para-PhP + C3H(Py)), 7.88 (dt, 1H, C5H(Py), J
1
1
= 7.6, 4J
1
1
=
3
H–
H
H–
H
ν(B–O) + ν(B–F), 1542, 1580sh ν(CvN), 1602 δ(N–H). UV-vis 1.5), 8.02 (dd, 4H, ortho-PhP, 3J
(CH2Cl2): λmax, nm (ε × 10−3, mol−1 L cm−1): 260(56), 288(30), 1H, C6H(Py), 3J = 5.0). 13C{1H} NMR (CD2Cl2) δ, ppm; J, Hz:
307(16), 356(5.9), 415(8.1), 468(15), 497(39), 548(10).
40.33 (s, CH2Py), 45.99 (s, CH2N), 122.46 (s, C3(Py)), 124.37 (s,
[Pd(FeBd2(((C6H5)2P(S))(2-NCH2Py)Gm)(BF)2)Cl]. Complex C5(Py)), 126.51 (d, 1J13 31 = 89.5, ipso-PhP), 127.76, 127.81
FeBd2(((C6H5)2P(S))(2-NHCH2Py)Gm)(BF)2 (0.138
g, (both s, ortho-Ph(Bd)), 128.96 (d, 3J13 31 = 14.3, meta-PhP),
1
1
= 7.3, 3J
1
31 = 15.0), 8.61 (d,
H–
H
H– P
1
1
H–
H
C–
P
C–
P
0.138 mmol) was dissolved in dichloromethane (2 ml) and a 129.13, 129.30 (both s, ipso-Ph(Bd)), 129.79, 129.83 (both s,
solution of Pd(C6H5CN)2Cl2 (0.053 g, 0.138 mmol) in dichloro- para-Ph(Bd)), 130.29, 130.47 (both s, meta-Ph(Bd)), 132.56 (d,
methane (1 ml) and triethylamine (0.019 ml, 0.138 mmol) 2J13 31 = 12.1, ortho-PhP), 133.47 (d, 4J13 31 = 3.3, para-PhP),
C–
P
C–
P
1
were added. The reaction mixture was stirred for 2 h and left 139.39 (s, C4(Py)), 148.55 (d, J13 31 = 75.5, PCvN), 151.04 (s,
C–
P
2
overnight. The precipitate formed was filtered off, washed with C6(Py)), 155.49 (d, J13 31 = 15.0, NCvN), 155.76, 157.88 (both
C–
P
dichloromethane (2 ml, in two portions) and dried in vacuo. s, PhCvN), 159.09 (s, C2(Py)). 31P{1H} NMR (CD2Cl2) δ, ppm:
Yield: 0.142 g (90%). The product was additionally purified by 31.18. 19F{1H} NMR (CD2Cl2) δ, ppm; J, Hz: −167.07, −168.61
preparative TLC on silica gel (eluent: dichloromethane–hexane (both q, 1J11 19 = 15.0). 11B{1H} NMR (CD2Cl2) δ, ppm; J, Hz:
B–
F
1
1 : 1 mixture). The major elute was evaporated to dryness, 3.30, 3.42 (both d, J11 19 = 15.0). IR (KBr) ν/cm−1: 910 m, 923,
B–
F
washed with hexane and dried in vacuo. Yield: 0.13 g (84%). 941 m, 1000, 1058, 1111, 1159, 1173 ν(N–O), 1209 m ν(B–O) +
Anal. Calc. for C48H36N8O6B2ClF2FePPdS (%): C, 50.52; H, 3.18; ν(B–F), 1544 m ν(CvN) + δ(N–H), 1580sh ν(CvN). UV-vis
N, 9.82; S, 2.81. Found (%): C, 50.53; H, 3.29; N, 9.69; S, 2.66. (CH2Cl2): λmax, nm (ε × 10−3, mol−1 L cm−1): 237(51), 271(2.4),
MS (MALDI-TOF) m/z (I, %): (positive range) 1105 (100) 298(3.9), 326(6.6), 386(3.0), 415(2.2), 438(0.7), 488(13), 577(6.4).
[M − Cl−]+•, 1141 (75) [M]+•, 1164 (15) [M + Na+]+, 1180 (5)
1
X-ray crystallography
[M + K+]+; (negative range) – 1141 [M]−•. H NMR (CD2Cl2): δ,
ppm; J, Hz: 5.14 (s, 2H, CH2), 7.32–7.47 (m, 20 + 1H, Ph(Bd) + Single crystals of the clathrochelates FeBd2(((C6H5)2P(S))ClGm)-
3
4
C5H(Py)), 7.54 (dt, 1H, C3H(Py), J
(dt, 1H, C4H(Py), 3J = 7.7, 4J
meta- + para-PhP), 8.00 (dd, 4H, ortho-PhP, 3J
15.2), 8.92 (d, 1H, C6H(Py), 3J = 5.0). 13C{1H} NMR (CD2Cl2) [FeBd2(((C6H5)2P(S))Gm)(BF)2]2(NH(CH2)5NH)·3.5 CH2Cl2 and
δ, ppm; J, Hz: 63.36 (s, CH2N), 119.74 (s, C3(Py)), 122.61 (s, two
palladium(II) complexes [Pd(FeBd2(((C6H5)2P(S))(2-
1
1
= 7.7, J
1
1
= 1.5), 7.86 (BF)2·CH2Cl2, FeBd2(((C6H5)2P(S))(n-C4H9NH)Gm)(BF)2·2 CH2Cl2,
H–
H
H–
H
1
1
1
1
= 1.5), 7.63–7.80 (m, 6H, FeBd2(((C6H5)2P(S))(2-NHCH2Py)Gm)(BF)2·C4H10O·CH2Cl2, FeBd2-
H–
H
H–
H
1
1
= 7.2, 3J
1
31
=
P
(((C6H5)2P(S))(CH3SCH2CH2NCH3)Gm)(BF)2·2
CHCl3
and
H–
H
H–
1
1
H–
H
C5(Py)), 126.05 (d, 1J13 31 = 89.5, ipso-PhP), 127.79, 127.89 NCH2Py)Gm)(BF)2)Cl]·CH2Cl2·H2O and [Pd(FeBd2(((C6H5)2P(S))-
C–
P
(both s, ortho-Ph(Bd)), 129.08 (s, ipso-Ph(Bd)), 129.13 (d, 3J13 31
(2-NCH2CH2Py)Gm)(BF)2)Cl]·2 CH2Cl2 with N,S-donor macro-
C–
P
= 13.9, meta-PhP), 129.31 (s, ipso-Ph(Bd)), 129.87, 129.92 (both bicyclic ligands were grown from their saturated solutions in
s, para-Ph(Bd)), 130.30, 130.55 (both s, meta-Ph(Bd)), 132.34 (d, dichloromethane–hexane, chloroform–heptane, diethyl ether–
2J13 31 = 11.7, ortho-PhP), 133.65 (d, 4J13 31 = 2.9, para-PhP), dichloromethane and diethyl ether–hexane mixtures at room
C–
P
C–
P
1
138.98 (s, C4(Py)), 148.06 (d, J13 31 = 74.5, PCvN), 148.18 (s, temperature. The intensities of reflections were measured at
C–
P
C6(Py)), 155.62 (br. s, NCvN), 155.84, 157.97 (both s, PhCvN), 100(2) K with a Bruker Apex II DUO diffractometer using Cu-
165.21 (s, C2(Py)). 31P{1H} NMR (CD2Cl2) δ, ppm: 31.59. 19F{1H} Kα radiation for FeBd2(((C6H5)2P(S))(2-NHCH2Py)Gm)(BF)2 (λ =
1
NMR (CD2Cl2) δ, ppm; J, Hz: −166.13, −169.31 (both q, J11 19
1.54178 Å, microfocus tube with multilayer optics) and Mo-Kα
B–
F
= 12.5). 11B{1H} NMR (CD2Cl2) δ, ppm; J, Hz: 3.25, 3.57 (both radiation for the other X-rayed cage compounds (λ = 0.71073 Å,
d, 1J11 19 = 12.5). IR (KBr) ν/cm−1: 904 m, 941, 954, 1058, 1109, graphite monochromator). Absorption corrections were per-
B–
F
1172 ν(N–O), 1205 m ν(B–O) + ν(B–F), 1544, 1574 ν(CvN), 1556 formed with the SADABS program,20 using multipole measure-
δ(N–H). UV-vis (CH2Cl2): λmax, nm (ε × 10−3, mol−1 L cm−1): ments of equivalent reflections. The structures were solved by
257(34), 287(17), 331(6.4), 428(5.8), 488(12), 525(7.5), 575(4.4), the direct method and refined by full-matrix least squares
605(3.2).
method against F2 of all data, using SHELXTL PLUS software21
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Dalton Transactions
and OLEX2 program.22 Non-hydrogen atoms were found on
difference Fourier maps and refined with anisotropic displace-
ment parameters with an exception of disordered ones. A
methyl moiety of methylsulfide group, one phenyl ring and a
solvate chloroform molecule in the crystal of FeBd2(((C6H5)2-
P(S))(CH3SCH2CH2NCH3)Gm)(BF)2·2CHCl3 are disordered over
two parts with 0.75 : 0.25 (for carbon and hydrogen atoms) or
0.5 : 0.5 (for chlorine atoms) site occupancies and were refined
in isotropic approximation for carbon atoms. The unit cells of
the crystal of clathrochelates FeBd2(((C6H5)2P(S))(2-NHCH2Py)-
Gm)(BF)2 and [FeBd2(((C6H5)2P(S))Gm)(BF)2]2(NH(CH2)5NH)
contain 2 and 3.5 highly disordered solvate dichloromethane
molecules, respectively, which have been treated as a diffuse
contribution to the overall scattering without specific atom
positions by SQUEEZE/PLATON.23 The chemical formula,
formula weight and Dcalc were calculated taking these solvate
molecules into account. In order to avoid strong anisotropy of
some atoms in the molecules FeBd2(((C6H5)2P(S))(n-C4H9NH)-
Gm)(BF)2, [Pd(FeBd2(((C6H5)2P(S))(2-NCH2Py)Gm)(BF)2)Cl] and
2 S. Viswanathan, Y. Z. Voloshin, H. Radecka and J. Radecki,
Electrochim. Acta, 2009, 54, 5431–5438.
3 Y. Z. Voloshin, A. S. Belov, O. A. Varzatskii,
A. V. Vologzhanina, S. Viswanathan, J. Radecki and
Y. N. Bubnov, Inorg. Chim. Acta, 2009, 362, 2982–2988.
4 (a) O. Pantani, S. Naskar, R. Guillot, M. Millet,
E. Anxolabéhère-Mallart and A. Aukauloo, Angew. Chem.,
Int. Ed., 2008, 47, 9948–9950; (b) Y. Z. Voloshin,
A. V. Dolganov, O. A. Varzatskii and Y. N. Bubnov, Chem.
Commun., 2011, 47, 7737–7739; (c) M. T. D. Nguyen,
M.-F. Charlot and A. Aukauloo, J. Phys. Chem. A, 2011, 115,
911–922; (d) P. Millet, N. Mbemba, S. A. Grigoriev,
V. N. Fateev, A. Aukauloo and C. Etiévant, Int. J. Hydrogen
Energy, 2011, 36, 4134–4142; (e) Y. Z. Voloshin, A. S. Belov,
A. V. Vologzhanina, G. G. Aleksandrov, A. V. Dolganov,
V. V. Novikov, O. A. Varzatskii and Y. N. Bubnov, Dalton
Trans., 2012, 41, 6078–6093; (f) E. Anxolabéhère-Mallart,
C. Costentin, M. Fournier, S. Nowak, M. Robert and
J.-M. Savéant, J. Am. Chem. Soc., 2012, 134, 6104–6107;
(g) A. V. Dolganov, A. S. Belov, V. V. Novikov,
A. V. Vologzhanina, A. Mokhir, Y. N. Bubnov and
Y. Z. Voloshin, Dalton Trans., 2013, 42, 4373–4376.
[Pd(FeBd2(((C6H5)2P(S))(2-NCH2CH2Py)Gm)(BF)2)Cl],
ISOR
command was applied. Besides, in the latter case SADI
command was used for the refinement of the solvate dichloro-
methane molecules, which are disordered over two sites. The
positions of hydrogen atoms were calculated and included in
the refinement in isotropic approximation by the riding model
with the Uiso(H) = 1.2Ueq(C), where Ueq(C) are equivalent
thermal parameters of parent atoms.
5 B. Burdukov, M. A. Vershinin, N. V. Pervukhina,
E. G. Boguslvaskii, I. V. Eltsov, L. A. Shundrin,
S. L. Selector, A. V. Shokurov and Y. Z. Voloshin, Inorg.
Chem. Commun., 2014, 44, 183–187.
6 (a) Y. Z. Voloshin, O. A. Varzatskii, K. Y. Zhizhin,
N. T. Kuznetsov and Y. N. Bubnov, Russ. Chem. Bull., 2006,
55, 22–25; (b) Y. Z. Voloshin, S. Y. Erdyakov,
I. G. Makarenko, E. G. Lebed, T. V. Potapova, S. V. Svidlov,
Z. A. Starikova, E. V. Polshin, M. E. Gurskii and
Y. N. Bubnov, Russ. Chem. Bull., 2007, 56, 1787–1794;
(c) S. Y. Erdyakov, Y. Z. Voloshin, I. G. Makarenko,
E. G. Lebed, T. V. Potapova, A. V. Ignatenko,
A. V. Vologzhanina, M. E. Gurskii and Y. N. Bubnov, Inorg.
Chem. Commun., 2009, 12, 135–139; (d) N. T. Kuznetsov,
I. G. Belaya, A. V. Dolganov, G. E. Zelinsky, E. Y. Matveev,
K. Y. Zhizhin, Y. Z. Voloshin and Y. N. Bubnov, Russ. Chem.
Bull., 2011, 60, 2518–2521.
The main crystallographic and refinement parameters are
listed in Tables S1 and S2 (see the ESI¶).
Catalytic experiments
General procedure. An aryl halide (0.5 mmol), phenylboro-
nic acid (0.079 g, 0.65 mmol), K3PO4 (0.159 g, 0.75 mmol) and
a palladium-containing clathrochelate catalyst (0.005 mmol)
were dissolved/suspended in DMF (15 ml) under argon and
the stirred reaction mixture was heated at 100 °C for 4 h. Then,
the reaction mixture was cooled to r.t. and water (3 ml) was
added. The organic products were extracted with benzene
(10 ml), the extract was dried with Na2SO4 and then analyzed
by a GC method.
7 V. V. Novikov, O. A. Varzatskii, V. V. Negrutska,
Y. N. Bubnov, L. G. Palchykovska, I. Y. Dubey and
Y. Z. Voloshin, J. Inorg. Biochem., 2013, 124, 42–45.
8 Y. Voloshin, O. Varzatskii, V. Novikov and Y. Bubnov, Proc.
9th EUROBIC, Wroclaw, Poland, 2–6 September, 2008, 71–
76.
Acknowledgements
This work was supported by the RFBR (grants 12-03-31581 and
12-03-90431), RAS (programs 6 and P8) and the Russian
State Atomic Energy Corporation “ROSATOM” (project
D.4f.43.90.13.1053).
9 Y. Voloshin, O. Varzatskii, S. Shul’ga, V. Novikov, A. Belov,
I. Makarenko, I. Dubey, D. Krivorotenko, V. Negrutska,
K. Zhizhin, N. Kuznetsov and Y. Bubnov, Proc. 10th
EUROBIC, Thessaloniki, Greece, 22–26 June, 2010, 29–38.
10 (a) Y. Z. Voloshin, O. A. Varzatskii, T. E. Kron, V. K. Belsky,
V. E. Zavodnik and A. V. Palchik, Inorg. Chem., 2000, 39,
1907–1918; (b) Y. Z. Voloshin, V. E. Zavodnik,
O. A. Varzatskii, V. K. Belsky, A. V. Palchik,
N. G. Strizhakova, I. I. Vorontsov and M. Y. Antipin,
J. Chem. Soc., Dalton Trans., 2002, 1193–1202;
(c) Y. Z. Voloshin, O. A. Varzatskii, A. V. Palchik,
Notes and references
1 Y. Z. Voloshin, N. A. Kostromina and R. Krämer, Clathro-
chelates: synthesis structure and properties, Elsevier, Amster-
dam, 2002.
9688 | Dalton Trans., 2014, 43, 9677–9689
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Dalton Transactions
Paper
N. G. Strizhakova, I. I. Vorontsov, M. Yu. Antipin,
D. I. Kochubey and B. N. Novgorodov, New J. Chem., 2003,
27, 1148–1155; (d) Y. Z. Voloshin, O. A. Varzatskii,
Adv., 2013, 3, 24484–24491; (d) S. Biju, N. Gopakumar, J.-C.
G. Bünzli, R. Scopelliti, H. K. Kim and M. L. P. Reddy,
Inorg. Chem., 2013, 52, 8750–8758.
T. E. Kron, V. K. Belsky, V. E. Zavodnik, N. G. Strizhakova, 13 (a) J. Dupont, C. S. Consorti and J. Spencer, Chem. Rev.,
V. A. Nadtochenko and V. A. Smirnov, J. Chem. Soc., Dalton
Trans., 2002, 1203–1211; (e) Y. Z. Voloshin, O. A. Varzatskii,
I. I. Vorontsov and M. Y. Antipin, Angew. Chem., Int. Ed.,
2005, 105, 2527–2571; (b) R. Martin and S. L. Buchwald,
Acc. Chem. Res., 2008, 41, 1461–1473; (c) D. Mc Cartney and
P. J. Guiry, Chem. Soc. Rev., 2011, 40, 5122–5150.
2005, 44, 3400–3402; (f) O. A. Varzatskii, Y. Z. Voloshin, 14 (a) T. E. Barder, S. D. Walker, J. R. Martinelli and
S. V. Korobko, S. V. Shulga, R. Krämer, A. S. Belov,
A. V. Vologzhanina and Y. N. Bubnov, Polyhedron, 2009, 28,
3431–3438; (g) Y. Z. Voloshin, O. A. Varzatskii,
V. V. Novikov, N. G. Strizhakova, I. I. Vorontsov,
A. V. Vologzhanina, K. A. Lyssenko, G. V. Romanenko,
V. I. Ovcharenko and Y. N. Bubnov, Eur. J. Inorg. Chem.,
2010, 5401–5415; (h) O. A. Varzatskii, Y. Z. Voloshin,
P. A. Stuzhin, S. V. Shul’ga, S. V. Volkov, A. V. Vologzhanina,
E. G. Lebed and Y. N. Bubnov, Inorg. Chem. Commun., 2011,
14, 1504–1507; (i) A. S. Belov, A. I. Prikhod’ko,
V. V. Novikov, A. V. Vologzhanina, Y. N. Bubnov and
S. L. Buchwald, J. Am. Chem. Soc., 2005, 127, 4685–4696;
(b) F. Alonso, I. P. Beletskaya and M. Yus, Tetrahedron,
2008, 64, 3047–3101; (c) F. Schneider, A. Stolle,
B. Ondruschka and H. Hopf, Org. Process Res. Dev., 2009,
13, 44–48; (d) S. E. Lyubimov, A. A. Vasil’ev,
A. A. Korlyukov, M. M. Ilyin, S. A. Pisarev, V. V. Matveev,
A. E. Chalykh, S. G. Zlotin and V. A. Davankov, React. Funct.
Polym., 2009, 69, 755–758; (e) V. A. Kozlov,
D. V. Aleksanyan, Y. V. Nelyubina, K. A. Lyssenko,
P. V. Petrovskii, A. A. Vasil’ev and I. L. Odinets, Organo-
metallics, 2011, 30, 2920–2932.
Y. Z. Voloshin, Eur. J. Inorg. Chem., 2012, 4507–4514; 15 (a) M. I. Kabachnik and T. A. Mastryukova, Phase-Transfer
( j) Y. Z. Voloshin, I. G. Belaya, A. S. Belov, V. E. Platonov,
A. M. Maksimov, A. V. Vologzhanina, Z. A. Starikova,
A. V. Dolganov, V. V. Novikov and Y. N. Bubnov, Dalton
Catalysis in Organophosphorus Chemistry, OPA, Amsterdam,
1996; (b) G. Ilia, L. Macarie, E. Bálint and G. Keglevich,
Catal. Rev. Sci. Eng., 2011, 53, 152–198.
Trans., 2012, 41, 737–746; (k) Y. Z. Voloshin, A. S. Belov, 16 (a) L. Tschugaeff, Ber. Dtsch. Chem. Ges., 1906, 39, 3190–
O. A. Varzatskii, S. V. Shul’ga, P. A. Stuzhin, Z. A. Starikova,
E. G. Lebed and Y. N. Bubnov, Dalton Trans., 2012, 41, 921–
928.
3209; (b) Comprehensive coordination chemistry II: from
biology to nanotechnology, ed. J. A. McCleverty and
T. J. Meyer, Elsevier, Amsterdam, 2004.
11 (a) B. Bibal, J.-P. Declercq, J.-P. Dutasta, B. Tinant and 17 M. A. Vershinin, A. B. Burdukov, E. G. Boguslavskii,
A.-G. Valade, Tetrahedron, 2003, 59, 5849–5854;
(b) A. Ouady, O. Klimchuk, C. Gallard and J. Billard, Green
Chem., 2007, 9, 1160–1062; (c) E. V. Matveeva, E. V. Sharova,
N. V. Pervukhina, N. V. Kuratieva, I. V. Eltsov,
V. A. Reznikov, O. A. Varzatskii, Y. Z. Voloshin and
Y. N. Bubnov, Inorg. Chim. Acta, 2011, 366, 91–97.
A. N. Turanov, V. K. Karandashev and I. L. Odinets, Cent. 18 Y. Z. Voloshin, A. S. Belov, Z. A. Starikova and
Eur. J. Chem., 2012, 10, 1933–1941; (d) A. E. V. Gorden, A. V. Vologzhanina, Russ. Chem. Bull., 2013, 62, 1858–1865.
M. A. DeVore and B. A. Maynard, Inorg. Chem., 2013, 52, 19 G. Ponzio and F. Baldrocco, Gazz. Chim. Ital., 1930, 60,
3445–3458. 415–420.
12 (a) J. Andres and A.-S. Chauvin, Inorg. Chem., 2011, 50, 20 G. M. Sheldrick, SADABS v.2.01, Bruker/Siemens Area Detec-
10082–10090; (b) D. V. Aleksanyan, V. A. Kozlov,
tor Absorption Correction Program, Bruker AXS, Madison,
Y. V. Nelyubina, K. A. Lyssenko, L. N. Puntus, E. I. Gutsul,
Wisconsin, USA, 1998.
N. E. Shepel, A. A. Vasil’ev, P. V. Petrovskii and 21 G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystal-
I. L. Odinets, Dalton Trans., 2011, 40, 1535–1546; logr., 2008, 64, 112–122.
(c) D. V. Aleksanyan, V. A. Kozlov, B. I. Petrov, 22 O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard
T. V. Balashova, A. P. Pushkarev, A. O. Dmitrienko, and H. Puschmann, J. Appl. Crystallogr., 2009, 42, 339–341.
G. K. Fukin, A. V. Cherkasov, M. N. Bochkarev, 23 A. L. Spek, Acta Crystallogr., Sect. D: Biol. Crystallogr., 2009,
N. M. Lazarev, Y. A. Bessonova and G. A. Abakumov, RSC
65, 148–155.
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