Heterobinuclear Zn-Ln and Ni-Ln Complexes with Schiff-Base and Carbacylamidophosphate Ligands: Synthesis, Crystal Structures, and Catalytic Activity

Article abstract of DOI:10.1002/ejic.201402224

The reaction of Salen-like Zn^II and Ni^II precursors with carbacylamidophosphate lanthanide moieties yields six new types of 3d-4f compounds. The complexes were characterized by means of ¹H, ³¹P NMR and IR spectr

Full text of DOI:10.1002/ejic.201402224

FULL PAPER
DOI:10.1002/ejic.201402224
Heterobinuclear Zn–Ln and Ni–Ln Complexes with Schiff-
Base and Carbacylamidophosphate Ligands: Synthesis,
Crystal Structures, and Catalytic Activity
[
a]
[a]
Oleksiy V. Amirkhanov,* Olesia V. Moroz,
[a]
[a]
[a]
Kateryna O. Znovjyak, Tetiana Yu. Sliva, Larysa V. Penkova,
[b]
[c]
[d]
Tetyana Yushchenko, Lukasz Szyrwiel, Irina S. Konovalova,
[d]
[d,e]
Viktoriya V. Dyakonenko, Oleg V. Shishkin,
Vladimir M. Amirkhanov*[
and
a]
Keywords: Heterometallic complexes / Kinetics / Lanthanides / N,O-ligands / Structure elucidation
The reaction of Salen-like ZnII and NiII precursors with car- whereas the ZnII ion has a tetragonal-pyramidal geometry.
bacylamidophosphate lanthanide moieties yields six new
types of 3d–4f compounds. The complexes were charac-
terized by means of H, P NMR and IR spectroscopy, ele- coordination compounds in the reaction of intramolecular hy-
The coordination number of lanthanides is nine or ten. Hy-
drolytic activities of some heterobimetallic Zn–Ln and Ni–Ln
1
31
mental analysis, ESI mass spectrometry, and X-ray diffraction
analysis. Depending on the Schiff base ligands, the Ni ion
drolytic degradation of the 2-(hydroxypropyl)-p-nitrophenyl
phosphate were investigated.
II
adopts either a square-planar or an octahedral geometry,
Introduction
uclear complexes.[3–6] However, the investigations in the
field of 3d–4f heterobinuclear compounds have mainly fo-
Bidentate chelate ligand systems with oxygen donor
atoms such as β-diketones and their derivatives are widely
represented in modern coordination chemistry because they
form numerous complexes with s-, p-, d-, and f-metal ions.
cused on their applications in magnetism and lumines-
[7–15]
cence,
whereas their application in areas such as cataly-
sis has, to our knowledge, not been reported.
Recently, we have studied heteroleptic coordination com-
pounds with β-diketone derivatives as carbacylamidophos-
Lanthanide-based systems Ln(L) with these types of li-
3
gands demonstrate coordination unsaturation because of
the large coordination numbers of lanthanide ions.[ One
of the ways to eliminate such unsaturation is the incorpora-
tion of additional ligands into the complex molecules. For
example, a transition-metal complex with extra donor coor-
dination centers can be used for this purpose. In this regard,
much effort has been devoted to the coordination chemistry
of tetradentate and hexadentate Salen-like 3d–4f heterobin-
1,2]
phates (CAPh), containing the functional fragment C(O)-
[16,17]
NHP(O).
Here, we report the synthesis, structural
characterization, and catalytic properties of new binuclear
d–4f complexes based on unsaturated lanthanide moieties
3
II
II
with CAPh, and complexes of Zn and Ni with Schiff
bases as additional ligands (Scheme 1).
[
a] Department of Chemistry, Taras Shevchenko National
University of Kyiv,
6
4/13, Volodymyrska Street, Kyiv 01601, Ukraine
E-mail: alexey.amirkhanov@gmail.com
v_amirkhanov@yahoo.com
www.chem.univ.kiev.ua
[
b] Fachbereich Chemie, Universität Konstanz,
7
8457 Konstanz, Germany
[
c] Department of Chemistry of Drugs, Wrocław Medical
University,
ul. Borowska 211, 50-552 Wrocław, Poland
d] SSI “Institute for Single Crystals”, National Academy of
Science of Ukraine,
[
6
0 Lenina Ave., Kharkiv 61001, Ukraine
[
e] Department of Inorganic Chemistry, V. N. Karazin Kharkiv
National University,
4
Svobody Sq., Kharkiv 61077, Ukraine
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201402224.
Scheme 1. Precursors for syntheses of 3d–4f complexes.
Eur. J. Inorg. Chem. 2014, 3720–3730
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Combining 3d and 4f metals in one molecule, we have
Numerous coordination compounds of s-, p-, d- and f-
tested the ability of the system to catalyze the intramolecu- metals based on CAPh have been obtained to date, and
lar transesterification of 2-(hydroxypropyl)-p-nitrophenyl it was demonstrated that IR spectroscopy is suitable for a
phosphate (HPNP), which has been extensively employed preliminary analysis of the coordination modes of the li-
[
27–29]
as an RNA model substrate. In many cases, dinuclear spe- gands in these complexes.
cies are more reactive than mononuclear species, because CAPh ligands in the anionic form coordinate to the
one metal ion of the dinuclear system can bind the substrate metal ions mostly in a bidentate manner through oxygen
–
and the second can bind an OH group, which can act as a atoms of the phosphoryl and carbonyl groups with the for-
nucleophile. Various phosphoesterases are known to con- mation of six-membered chelate cycles, which can be in-
[
18–22]
tain one or more 3d-metal ions within their active site.
ferred from the bathochromic shifts of the bands of the val-
Lanthanide complexes are highly reactive for the cleavage ence vibrations of phosphoryl ν(PO) and carbonyl ν(CO)
of aryl phosphodiesters[
neutral solutions. With the aim of testing the influence of monodentate manner. Thus, only the absorption band of
d and 4f metal ions combined in a single molecule, we the phosphoryl group undergoes the low frequency shift.
decided to study our binuclear 3d–4f complexes as catalysts Interpretation of the IR spectra of the synthesized binuclear
23–25]
and diribonucleotides
[26]
in groups. In the neutral form, ligands usually coordinate in a
3
1
2
for the hydrolysis of HPNP.
compounds based on HL and HL is more complex due
to the superposition of the characteristic absorption bands
of CAPh ligands and of the Schiff bases. In the IR spectra
1
2
Results and Discussion
of the free HL and HL , ν(CO) band has a maximum at
–1
[30,31]
1
715 cm–1 and 1725 cm , respectively.
For the synthe-
Synthesis and Spectroscopic Characterization
sized complexes, an intense asymmetric broad band is ob-
served in the region of 1605–1655 cm , which can be re-
lated to the superposition of the valence vibrations of
–1
With the aim of obtaining new 3d–4f coordination com-
pounds, M(Ve) or M(Vp) complexes (M = Zn , Ni , H Ve
II
II
2
1 –
2 –
ν(CO) [from (L ) or (L ) ] and ν(CN) (from the Schiff
=
6,6Ј-{(1E,1ЈE)-[ethane-1,2-diylbis(azanylylidene)]bis-
1
bases) (Table S1). In the IR spectra of the neat ligands HL
(methanylylidene)}bis(2-methoxyphenol) and H Vp = 6,6Ј-
2
2
–1
and HL , the band of ν(PO) locates at 1205 and 1235 cm ,
respectively. In binuclear complexes, the value of ν(PO) re-
veals a bathochromic shift and splitting, and falls in the
{
(1E,1ЈE)-[propane-1,3-diylbis(azanylylidene)]bis(methan-
ylylidene)}bis(2-methoxyphenol)) were used as additional
1
ligands for the coordinatively unsaturated Ln(L ) or
3
–1
range of 1170–1196 cm . Splitting or broadening of the
2
1
Ln(L ) {HL = N-[bis(dimethylamino)phosphoryl]-2,2,2-
3
ν(PO) band presumably appears due to non-equivalently
coordinated CAPh ligands. The exact assignment of these
bands is difficult to achieve without quantum chemical cal-
culations, which is outside the scope of this study. Accord-
ing to the bathochromic shifts for ν(CO) and ν(PO), we
2
trichloroacetamide and HL = N-[bis(diethylamino)phos-
phoryl]-2,2,2-trichloroacetamide} unit. The complexes
M(Ve) and M(Vp) were synthesized by the reaction between
equimolar amounts of the acetate of 3d-metal and H Ve or
2
H Vp in CH OH/CHCl and were used for the preparation
2
3
3
1
2
assume that HL and HL coordinate to the lanthanide ions
in the bidentate mode.
of 3d–4f complexes without isolation from the reaction mix-
ture. The solution of M(Ve) or M(Vp) was mixed with a
The intense bands with maxima at 1563–1585 cm–1 in the
1
2
methanol or 2-propanol solution of Ln(L ) or Ln(L ) ,
3
3
+
IR spectra of 1a-La, 1b-Eu, 2a-Ln, 2b-Ln, and 2c-Ln were
1
forming Zn–Ln and Ni–Ln complexes containing Ln(L ) ,
2
[32,33]
assigned to ν (CO) of the acetate anion.
In the case
2
+
1 2+
as
Ln(L ) , and Ln(L ) units. This fact can be explained by
2
of 1c-La and 1c-Nd, intense absorption bands in the range
the presence of the relatively bulky substituents N(Me) and
2
–1
of 1292–1472 cm indicate the presence of nitrate groups.
1
2
N(Et) in HL and HL , respectively. The variation of the
2
For the binuclear complexes, broadened bands at 1204–
molar ratio 1:1:3, 1:1:2 and 1:1:1 of the starting compounds
1
245 cm–1 are observed and assigned to ν(C –O) of
Ph
[
M(Schiff)/Ln(NO ) /NaL] leads to similar results. The syn-
3 3
[34,35]
Zn(Schiff) or Ni(Schiff).
thesized binuclear complexes are summarized in Table 1.
II
The synthesized 3d–4f compounds with diamagnetic Zn
III
1
31
and La ions were characterized by H and P NMR
spectroscopy and compared with the corresponding spectra
of HL , HL , H Ve, and H Vp (Table S2). In the H NMR
spectrum of HL , a doublet at δ = 2.77 ppm has a spin-spin
coupling constant of 10.4 Hz. In the case of HL , a triplet
Table 1. Synthesized 3d–4f complexes.
1
2
1
Complexes based on HL1
2 2
1
1
[
[
[
[
Zn(μ-Ve)La(L )
2
(μ-OAc)]
(1a-La)
(1b-Eu)
2
1
Zn(μ-Ve)Eu(L )
2
(μ-OAc)]MeOH·
(MeOH)(μ-OAc)]
1
Zn(μ-Ve)Eu(L )
2
and multiplet are detected at δ = 1.15 and 3.19 ppm, respec-
1
Ni(Ve)Ln(L )(NO
3
)
2
], Ln = La, Nd
(1c-Ln)
tively. In the spectrum of 1a-La, two doublets are observed
Complexes based on HL2
1
shifted upfield in comparison with the spectrum of HL .
2
This feature relates to the delocalization of π-electron den-
[
[
Zn(μ-Ve)Ln(L )
2
(μ-OAc)], Ln = La, Nd, Gd, Er
(2a-Ln)
2
sity in the ligand due to deprotonation and coordination to
Zn(μ-Vp)Ln(L )
2
(μ-OAc)], Ln = La, Nd, Eu, Dy, Er, (2b-Ln)
III
Lu
[
Er, Lu
the La ion. Two doublets in this region might correspond
Ni(μ-Vp)(MeOH)Ln(L2)
2
(μ-OAc)], Ln = La, Eu, Gd, (2c-Ln)
to the presence of nonequivalent phosphoryl ligands in the
molecule of the complex. A similar shift of the aliphatic
Eur. J. Inorg. Chem. 2014, 3720–3730
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protons is observed in the spectra of complexes 2a-La and shown in Figure 1, Figure 2, Figure 3, Figure 4, and Fig-
2
2
b-La based on HL .
ure 5, Figure S1, and Figure S2, and selected geometrical
Two broad signals in the 31P NMR spectra of 1a-La, 2a- parameters are listed in Table 4 and Table 5.
La, and 2b-La additionally confirm the nonequivalence of
phosphorus atoms of the coordinated ligands.
Crystal Structures of 1a-La, 2a-La, 2b-La, and 2b-Eu
1
In the H NMR spectra of H Ve and H Vp, there are
2
2
The crystal structures of the complexes are composed of
four and five types of signals, respectively, assigned to the
II
III
heterobinuclear units containing Zn and Ln ions, which
are connected by two bridging phenolate oxygen atoms of
protons of CH , CH , CH, and OH groups. Resonance
2
3
multiplets of the aromatic protons of H Ve and H Vp lie in
2
2
2–
2–
(
Ve) or (Vp) and an acetate anion. The ZnO La(Eu)
2
the range of 6.76–6.91 ppm and 6.80–6.94 ppm, respec-
tively. The spectra of 1a-La, 2a-La, and 2b-La contain all
expected bands of the Schiff bases. A singlet at 1.8–1.9 ppm
clearly indicates the presence of the acetate anion in the
complexes. Analysis of the integral intensities of the signals
fragment is not planar [angle between the O–Zn–O and O–
La(Eu)–O planes is 152.3°, 152.8°, 153.3 and 153.9° for 1a-
La, 2a-La, 2b-La, and 2b-Eu, respectively]. The coordina-
III
tion polyhedron of Ln is formed by four oxygen atoms of
1
Zn(Ve) or Zn(Vp), four oxygen atoms of bidentately coordi-
in the H NMR spectra of 1a-La, 2a-La, and 2b-La reveals
1
–
2 –
nated ligands (L ) or (L ) and an oxygen atom of a bridg-
the formation of the complexes with a molar ratio of the
1
–
2 –
ing linked acetate group, resulting a coordination number
Schiff base to (L ) or (L ) as 1:2.
III
of the Ln ion of nine (Figure 1, Figure 2, Figure S1 and
Figure S2).
The average length values of the La–O and Eu–O bonds
formed by the bridging phenolate groups are shorter than
Crystal Structures of Complexes
2–
Single crystals were obtained for 1a-La, 1b-Eu, 1c-La, the bonds observed for the methoxy groups of (Ve) or
2–
2
a-La, 2b-La, 2b-Eu, and 2c-La complexes. The selected (Vp) . Similar results were reported for related heterobinu-
[
36]
II
crystallographic data are summarized in Table 2 and clear β-diketonate complexes.
The Zn ion adopts a te-
Table 3. The molecular structures of the complexes are tragonal-pyramidal coordination geometry, where the equa-
Table 2. Crystal data and structure refinement of 1a-La, 1b-Eu, 1c-La.
Compounds
1a-La
1b-Eu
1c-La
Empirical formula
Formula weight
Temperature [K]
Wavelength [Å]
Crystal system
Space group
Unit cell dimensions
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C
32
H
45Cl
6
LaN
8
O
10
P
2
Zn
C
66
H
98Cl12Eu
2
N
16
O
22
P
4
Zn
2
24 3 7
C H30Cl LaN NiO12P
943.49
293(2)
1180.68
294(2)
0.71073
monoclinic
P2
2451.54
293(2)
0.71073
triclinic
0.71073
triclinic
¯
¯
P1
1
P1
11.656(2)
16.249(2)
13.366(3)
90
108.15(4)
90
2405.5(7)
2
1.630
14.785(3)
19.423(2)
19.715(2)
108.55(4)
107.02(2)
104.70(3)
4741.7(12)
2
9.130(2)
11.597(3)
18.346(4)
91.12(2)
98.70(2)
110.69(3)
1790.7(7)
2
γ [°]
Volume [Å ]
3
Z
D
calcd. [g/cm3]
1.717
2.284
2464
1.750
2.037
940
–1
Absorption coefficient [mm ]
F(000)
1.831
1184
Crystal size [mm]
θ range for data collection [°]
Index ranges
0.40ϫ 0.20ϫ 0.10
2.98–30.00
–16 Յ h Յ 15,
0.30ϫ 0.20ϫ 0.20
3.1–27.5
–18 Յ h Յ 19,
–24 Յ k Յ 25,
–25 Յ l Յ 25
41275
21054
11014
0.0627
7/1105
0.40ϫ 0.20ϫ 0.10
3.01–27.50
–11 Յ h Յ 11,
–15 Յ k Յ 12,
–23 Յ l Յ 23
14467
8086
2632
0.1155
5/448
–
–
22 Յ k Յ 22,
12 Յ l Յ 18
Reflections collected
Independent reflections
Reflections with IϾ2σ(I)
R(int)
Restraints/parameters2
Goodness-of-fit on F
Final R indices [IϾ2σ(I)]
25262
7217
4853
0.0320
14/565
0.880
0.787
0.608
R
wR
1
= 0.0470,
= 0.1029
= 0.0735,
= 0.1111
R
wR
1
= 0.0489,
= 0.0804
= 0.0726,
= 0.1098
R
1
= 0.0552,
= 0.0630
= 0.1858,
2
wR = 0.0798
2
2
wR
2
R indices (all data)
R
1
R
1
R
1
wR
2
wR
2
–3
Largest diff. peak and hole [eÅ ]
CCDC reference number
1.08 and –0.43
985567
1.435 and –1.248
985568
0.920 and –0.674
985564
Eur. J. Inorg. Chem. 2014, 3720–3730
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Table 3. Crystal data and structure refinement of 2a-La, 2b-La, 2b-Eu, and 2c-La.
Compounds
2a-La
2b-La
2b-Eu
2c-La
Empirical formula
C
O
40
H
61Cl
Zn
6
LaN
8
-
C
O
41
63Cl
Zn
6
LaN
8
-
C
O
41
63Cl
Zn
6
EuN
8
-
C
O
42
67Cl
Ni
6 8
LaN -
10
P
2
Formula weight
Temperature [K]
Wavelength [Å]
Crystal system
Space group
Unit cell dimensions
a [Å]
b [Å]
c [Å]
α [°]
1292.89
293(2)
0.71073
1306.91
100(2)
0.71073
1319.96
293(2)
0.71073
1332.30
294(2)
0.71073
orthorhombic
P2
monoclinic
P2 /c
monoclinic
P2 /c
monoclinic
P2 /n
1
2
1
2
1
1
1
1
14.794(2)
16.368(3)
23.092(3)
90
15.5670(5)
22.8383(9)
15.4462(5)
90
15.860(2)
22.508(2)
15.231(3)
90
13.849(3)
29.583(2)
15.064(2)
90
β [°]
γ [°]
Volume [Å ]
90
90
93.839(3)
90
5479.2(3)
4
1.584
1.616
92.01(3)
90
5433.8(14)
4
1.614
1.998
108.18(3)
90
5863.6(15)
4
1.509
1.426
3
5591.7(15)
4
1.536
1.583
2624
Z
D
calcd. [g/cm3]
–1
Absorption coefficient [mm ]
F(000)
2656
2680
2720
Crystal size [mm]
θ range for data collection [°]
Index ranges
0.40ϫ 0.20ϫ 0.10
2.92–30.00
–20 Յ h Յ 18,
0.20ϫ 0.05ϫ 0.05
2.87–27.50
–20 Յ h Յ 20,
–27 Յ k Յ 29,
–11 Յ l Յ 20
35115
12469
8260
0.0801
0/633
0.40ϫ 0.20ϫ 0.10
2.93–27.50
–20 Յ h Յ 20,
–29 Յ k Յ 29,
–19 Յ l Յ 19
44805
11765
4888
0.1745
16/620
0.40ϫ 0.20ϫ 0.10
2.93–30.00
–19 Յ h Յ 19,
–41 Յ k Յ 21,
–19 Յ l Յ 21
58654
16929
11249
0.0424
18/698
–
–
22 Յ k Յ 23,
32 Յ l Յ 32
Reflections collected
Independent reflections
Reflections with IϾ2σ(I)
R(int)
Restraints/parameters2
Goodness-of-fit on F
Final R indices [IϾ2σ(I)]
56429
8815
6291
0.1446
35/691
0.936
1.038
0.880
0.922
R
wR
1
= 0.0506,
= 0.1092
= 0.0720,
= 0.1150
R
wR
1
= 0.0640,
= 0.1235
= 0.1116,
= 0.1374
R
wR
1
= 0.097,
= 0.1942
= 0.1931,
= 0.2166
R
1
= 0.0384,
= 0.0729
= 0.0722,
2
wR = 0.0787
2
2
2
wR
2
R indices (all data)
R
1
R
1
R
1
R
1
wR
2
wR
2
wR
2
–3
Largest diff. peak and hole [eÅ ]
CCDC reference number
1.165 and –1.487
985566
1.968 and –1.022
985565
5.836 and –1.680
985570
0.821 and –0.614
985569
Figure 1. Molecular structure of 1a-La with atom numbering
scheme and 30% probability thermal ellipsoids. Hydrogen and
chlorine atoms are omitted for clarity.
Figure 2. Molecular structure of 2b-La with atom numbering
scheme and 50% probability thermal ellipsoids. Hydrogen and
chlorine atoms are omitted for clarity.
Eur. J. Inorg. Chem. 2014, 3720–3730
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Figure 3. Molecular structure of 1b-Eu with atom numbering scheme and 50% probability thermal ellipsoids. Hydrogen atoms not
involved in hydrogen bonding, chlorine, and carbon atoms of N(CH ) groups are omitted for clarity.
3 2
Figure 4. Molecular structure of 1c-La with atom numbering
scheme and 30% probability thermal ellipsoids. Hydrogen and
chlorine atoms are omitted for clarity.
Figure 5. Molecular structure of 2c-La with atom numbering
torial positions are occupied by two nitrogen and two oxy- scheme and 30% probability thermal ellipsoids. Hydrogen atoms
2
–
2–
not involved in hydrogen bonding and chlorine atoms are omitted
for clarity.
gen atoms of (Ve) or (Vp) , whereas the axial position is
II
occupied by the oxygen atom of the acetate anion. The Zn
ion is displaced from the N O plane by 0.566, 0.578, 0.466
2
2
and 0.453 Å for 1a-La, 2a-La, 2b-La, and 2b-Eu, respec-
tively. The bond lengths in the fragments Zn(Ve) and tions: C8–C9 (0.25:0.75) for 1a-La, Cl4–Cl6 (0.4:0.6), C8–
Zn(Vp) are comparable to the published data for similar C9 (0.4:0.6), C31–C32 (0.3:0.7), C33 (0.4:0.6), C34
[
37–39]
complexes.
(0.25:0.75), C35–C36 (0.5:0.5) for 2a-La, and C22–C23
In the complexes, 1a-La, 2a-La, and 2b-Eu, some of the (0.3:0.7), C24 (0.35:0.65), C25(0.5:0.5), C36 (0.15:0.85),
carbon and chlorine atoms are disordered over two posi- C37 (0.35:0.65) for 2b-Eu.
Eur. J. Inorg. Chem. 2014, 3720–3730
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Table 4. Selected bond lengths of 1a-La, 1b-Eu, and 1c-La.
a-La
1
1b-Eu
1c-La
A
B
La1–Zn1
La1–O6
La1–O1
La1–O2
La1–O7
La1–O8
La1–O10
La1–O9
La1–O11
La1–O5
Zn1–O1
Zn1–O2
Zn1–N1
Zn1–N2
Zn1–O3
3.465(2)
2.792(5)
2.495(6)
2.496(6)
2.727(6)
2.457(5)
2.489(6)
2.531(4)
2.488(7)
2.559(5)
2.011(6)
1.999(6)
2.019(8)
2.063(8)
1.980(5)
Eu1A–Zn1A
Eu1A–O1A
Eu1A–O2A
Eu1A–O3A
Eu1A–O4A
Eu1A–O7A
Eu1A–O10A
Eu1A–O8A
Eu1A–O9A
Eu1A–O6A
Zn1A–O2A
Zn1A–O3A
Zn1A–N1A
Zn1A–N2A
Zn1A–O5A
3.3960(9)
2.723(4)
2.388(3)
2.378(3)
2.657(4)
2.372(4)
2.346(3)
2.372(3)
2.413(4)
2.436(4)
2.021(3)
2.004(3)
2.025(5)
2.055(4)
1.988(4)
Eu1B–Zn1B
3.393(1)
2.729(4)
2.387(4)
2.391(3)
2.675(4)
2.320(4)
2.376(3)
2.421(3)
2.377(4)
2.417(4)
2.026(3)
2.001(4)
2.036(6)
2.042(4)
1.999(4)
La1–Ni1
La1–O6
La1–O2
La1–O1
La1–O10
La1–O12
La1–O11
La1–O3
La1–O4
La1–O7
La1–O9
Ni1–O1
Ni1–O2
Ni1–N1
Ni1–N2
3.575(1)
2.715(4)
2.560(4)
2.581(4)
2.721(5)
2.431(4)
2.459(5)
2.685(5)
2.607(5)
2.618(5)
2.653(6)
1.836(5)
1.810(5)
1.858(6)
1.814(6)
Eu1B–O1B
Eu1B–O2B
Eu1B–O3B
Eu1B–O4B
Eu1B–O7B
Eu1B–O10B
Eu1B–O8B
Eu1B–O9B
Eu1B–O6B
Zn1B–O2B
Zn1B–O3B
Zn1B–N1B
Zn1B–N2B
Zn1B–O5B
Table 5. Selected bond lengths of 2a-La, 2b-La, 2b-Eu, and 2c-La.
2a-La
2b-La
2b-Eu
2c-La
La1–Zn1
La1–O1
La1–O2
La1–O3
La1–O4
La1–O8
La1–O11
La1–O9
La1–O10
La1–O7
Zn1–O2
Zn1–O3
Zn1–N1
Zn1–N2
Zn1–O5
3.480(1)
2.737(4)
2.496(4)
2.501(4)
2.730(4)
2.434(4)
2.456(3)
2.520(4)
2.503(3)
2.551(4)
1.996(5)
2.005(4)
2.064(8)
2.051(7)
1.970(4)
La1–Zn1
La1–O2
La1–O1
La1–O3
La1–O4
La1–O5
La1–O7
La1–O6
La1–O8
La1–O10
Zn1–O1
Zn1–O3
Zn1–N1
Zn1–N2
Zn1–O9
3.595(1)
2.678(3)
2.498(3)
2.532(4)
2.651(3)
2.478(3)
2.458(4)
2.517(4)
2.535(4)
2.530(4)
2.073(4)
2.050(3)
2.085(4)
2.119(5)
1.964(4)
Eu1–Zn1
Eu1–O1
Eu1–O2
Eu1–O3
Eu1–O4
Eu1–O5
Eu1–O7
Eu1–O6
Eu1–O8
Eu1–O9
Zn1–O2
Zn1–O3
Zn1–N1
Zn1–N2
Zn1–O10
3.508(2)
La1–Ni1
La1–O1
La1–O2
La1–O4
La1–O7
La1–O9
La1–O11
La1–O8
La1–O10
La1–O6
Ni1–O2
Ni1–O4
Ni1–N1
Ni1–N2
Ni1–O5
Ni1–O3
3.526(1)
2.687(2)
2.470(2)
2.454(2)
2.697(2)
2.481(2)
2.626(2)
2.511(2)
2.541(2)
2.497(2)
2.052(2)
2.034(2)
2.051(2)
2.034(2)
2.028(2)
2.167(2)
2.619(7)
2.391(8)
2.429(8)
2.605(7)
2.357(8)
2.366(7)
2.446(7)
2.408(8)
2.455(8)
2.057(9)
2.067(8)
2.08(1)
2.063(9)
1.952(9)
ions represent a distorted tricapped trigonal prism and a
distorted monocapped square antiprism, respectively, ac-
Crystal Structure of 1b-Eu
[40]
cording to the geometrical standards of Guggenberger.
Despite the identical method of synthesis of 1a-La and
b-Eu, the molecular structures of the complexes differ. In
II
The coordination number of the Zn ion is five, and the
coordination environment is a slightly distorted tetragonal-
1
the latter, the asymmetric unit contains two independent
pyramidal (O N ) for both molecules. The equatorial plane
molecules A and B with different coordination environ-
3
2
III
of the pyramid is formed by two oxygen and two nitrogen
ments of the Eu ion (Figure 3).
2–
III
atoms of (Ve) , the axial position is occupied by the oxygen
The coordination environment of the Eu ion in mole-
II
atom of the acetate group. The deviation of Zn ion from
cule A of 1b-Eu is similar to that of 1a-La. The acetate
group in A additionally forms an intermolecular O–H···OЈ
hydrogen bond with the hydrogen atom of a non-coordi-
nated molecule of methanol (H···OЈ 1.99 Å, O–H···OЈ
the mean N O plane is 0.568 and 0.582 Å for A and B
2
2
molecules, respectively. The angles between the (OZnO) and
OEuO) planes containing the bridging oxygen atoms are
50.9° and 150.5° for A and B molecules, respectively. In
(
1
172°). In the case of B, the coordination sphere of EuO is
9
the complex, 1b-Eu, some of the carbon atoms are disor-
dered over two positions: C8B–C9B (0.5:0.5).
formed by four oxygen atoms of Zn(Ve), three oxygen
atoms of bidentately and monodentately coordinated (L )
1
–
ligands, and one oxygen atom of coordinated methanol. An
oxygen atom of the bridged acetate anion occupies the
ninth position. Furthermore, an intramolecular hydrogen
Crystal Structure of 1c-La
The crystal structure of the complex consists of heterobi-
1
III
bond between the CO group of the monodentate coordi- nuclear molecules [Ni(Ve)La(L )(NO ) ] in which the La
3
2
1
–
nated (L ) and the coordinated methanol molecule is ob- center has a decacoordination environment. In addition to
served (H···OЈ 1.84 Å, O–H···OЈ 161°) in molecule B. The the phenolate and methoxy oxygen atoms of Ni(Ve), four
III
III
coordination polyhedra of La (1a-La) and Eu (1b-Eu) oxygen atoms of two bidentately coordinated nitrate groups
Eur. J. Inorg. Chem. 2014, 3720–3730
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1
–
and two O atoms of bidentately coordinated (L ) complete Mass-Spectrometric Analysis of 2b-Nd, 2c-La, and 2c-Er
the coordination sphere (Figure 4). The La–O bond lengths
To study in solution the stability of the obtained binu-
of the four types are significantly different: the longest are
2
clear coordination compounds based on HL ligand, ESI
the La–O(methoxy) distances and the shortest are the La–
II
III
MS studies of 2b-Nd, 2c-La, and 2c-Er were undertaken in
acetonitrile.
O(P) (see Table 4). The Ni ···La separation is 3.575(1) Å.
II
The Ni ion is tetracoordinate by two imine nitrogen atoms
and two bridging phenolate oxygen atoms from the (Ve)2–
The ESI mass spectrum of the complex 2b-Nd in the pos-
itive range contains a signal with m/z 1252, assigned to the
anion and adopts a slightly distorted square-planar geome-
try. The Ni center deviates from the N O plane by
.005 Å. As expected, the Ni–N and Ni–O bond lengths are
quite similar to those of the individual complex [Ni(Ve)-
H O]. The angle between the (ONiO) and (OLaO) planes
involving two bridging oxygen atoms is 164.3°, and is larger
than in 1a-La, 1b-Eu, 2a-La, 2b-La, and 2b-Eu compounds.
2
+ +
II
moiety [Zn(Vp)Nd(L ) ] (Mcalc = 1252.05). The experi-
2
2
2
mentally observed isotope distribution in this spectrum is
in good agreement with the calculated model for the corre-
sponding species (Figure S3).
0
[
41]
2
Mass spectra of the coordination compounds 2c-La and
2
c-Er indicate peaks with m/z 1241 and 1268, respectively,
2
+ +
which were also assigned to the species [Ni(Vp)La(L ) ]
2
2
+ +
(Mcalc = 1241.05) and [Ni(Vp)Er(L ) ] (M
= 1268.08)
Crystal Structure of 2c-La
2
calc
(Figure S4, Figure S5).
The structural determination of 2c-La shows the exis-
tence of a heterodinuclear complex [Ni(μ-Vp)(MeOH)-
La(L ) (μ-OAc)] (Figure 5). The La ion is nine-coordi-
Thus, the ESI mass spectrometric studies in acetonitrile
of the synthesized complexes confirm the existence in solu-
2
III
2
2–
tion of heterodinuclear fragments comprising (Vp) ligand
nate by four oxygen atoms from the bridging Schiff base,
and phosphoryl ligands.
2
–
four oxygen atoms from two bidentate chelating (L ) li-
gands and the oxygen atom of the bridging acetate anion,
forming a distorted monocapped square-antiprismatic co-
ordination environment. The position of the facet is occu-
Kinetic Measurements
2
–
pied by the oxygen atom O7 of the (Vp) ligand. An intra-
Intramolecular transesterification of the phosphodiester
molecular O–H···O hydrogen bond is observed between the 2-(hydroxypropyl)-p-nitrophenyl phosphate (HPNP) pro-
PO group and the coordinated methanol molecule. The vides an excellent test for catalysis because the substrate is
Ni···La separation is 3.526(1) Å.
easily available and 4-nitrophenolate product (NP) can be
2
–
III
Two La–O(P) bond lengths of the (L ) are not equal detected spectrophotometrically (Scheme 2). Ln and 3d-
[
2.481(2) and 2.626(2) Å] and this difference might be ex- metal mediated hydrolytic reactions, including phosphatase-
plained by the participation of one of the PO group in the like activity, were studied in buffered aqueous solutions (or
formation of the hydrogen bond. in media with high water content) to closely mimic bio-
The Ni ion is coordinated by two oxygen atoms and logical conditions.[46–48]
II
two nitrogen atoms of the Schiff base. The methanol mole-
An initial screening of the hydrolytic activity of 2b-Ln
cule and the bridging acetate ligand complete formation of and 2c-Ln was carried out at pH 8.00, in dimethyl sulfoxide
II
III
a slightly distorted octahedral sphere N O . The Ni center (DMSO)/buffered water (1:1, v/v) at 25 °C, where Ln is
2
4
III
III
III
is displaced from the equatorial mean plane of N O by La , Eu , or Lu . These conditions roughly corre-
2
2
0.081 Å. The value of the angle between the Ni1–O2–O4 sponded to the maximum hydrolysis rates of the substrate,
and La1–O2–O4 planes is 167.5°, which is larger than those as follows from bell-shaped pH profiles: Figure 6 shows the
II
of Zn -containing complexes 2b-La and 2b-Eu, thus the pH profile for 2b-Eu. The DMSO/buffered water (1:1, v/v)
NiO La fragment is less bent.
system was chosen because the compounds had low solubil-
2
II
From the literature data, it is known that the Ni ion ity in water.
2–
has an octahedral environment in the case of (Vp) com-
The rate constants for the HPNP hydrolysis were ob-
[
42–44]
plexes
and a square-planar or pyramidal geometry tained by plotting the increase of NP absorbance at 405 nm
2
–
[45]
when (Ve) is used as precursor,
which correlates well as a function of time. The kinetic data for all complexes
show that the rate of hydrolysis is linearly dependent on the
with our data.
In the complex 2c-La, atoms Cl4–Cl6 and C36–C37 are complex concentration (Figure 7). Pseudo-first-order rate
disordered over two positions with equal occupancy ratios constants kobs defined by V = k [complex] . The results
0
obs
0
(0.5:0.5).
(Table 6) show that 2b-Lu is the most effective among the
Scheme 2. Intramolecular hydrolytic degradation of the 2-(hydroxypropyl)-p-nitrophenyl phosphate (HPNP) resulting in formation of the
cyclic phosphate (3-methyl-2,5-dioxaphospholan-2-ol 2-oxide) and the p-nitrophenolate ion.
Eur. J. Inorg. Chem. 2014, 3720–3730
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Michaelis–Menten method. As an example, the plot of the
initial reaction rate vs. the concentration of the substrate
for 2b-Eu is shown in Figure 8.
Figure 6. Effect of pH on HPNP hydrolysis rate mediated by 2b-
Eu. [HPNP] = 0.16 mm, [2b-Eu] = 0–0.16 mm at 25 °C, in DMSO/
buffered H O (1:1).
0
0
2
examined complexes. Calculated kobs for 2b-Ln and 2c-Ln Figure 8. Dependence of the initial reaction rate (V ) on the HPNP
0
lay in the order Lu Ͼ Eu Ͼ La and were comparable to concentration for the hydrolysis reaction promoted by 2b-Eu on
–
6
concentration; [2b-Eu]
0
= 8ϫ10 m, at 25 °C, pH 8.00, in DMSO/
those found for the phosphodiester and DNA hydrolysis
Tris·HCl buffer (1:1).
[
47,49–51]
promoted by di- and multi-nuclear metal complexes.
No significant hydrolysis of the test substrate occurred in
the absence of the complexes.
The kinetic data for other compounds are summarized in
Table 6. The initial reaction rate vs. concentration of HPNP
increases, suggesting formation of a complex–substrate in-
termediate. Analysis of the data for 2c-Lu reveals that the
Michaelis–Menten constant (KM = 0.47Ϯ0.09 mm) is
higher than other studied complexes, indicating less binding
affinity and therefore a higher catalytic rate constant [k
=
cat
(2.86Ϯ0.20)ϫ10–4 s ]. The highest binding affinity was
–1
observed for 2c-La (KM = 0.05Ϯ0.01 mm). Complexes 2b-
Lu and 2c-Lu showed higher catalytic efficiency than the
III
III
complexes of La and Eu . These three lanthanides have
the same electron charge, but because it has the smallest
III
radius, Lu is the stronger Lewis acid, which presumably
helps to deprotonate the coordinated water molecule form-
ing an active hydroxyl group. The effect of 3d-metal ion
may be associated with a ligand substitution mechanism:
II
the five-coordinate Zn ion undergoes associative substitu-
II
tion but the six-coordinate Ni ion follows dissociative sub-
Figure 7. Dependence of the reaction rate on the concentration of
the complex 2b-Eu for the hydrolysis of HPNP; [HPNP]
0
=
stitution. This difference results in higher values for kobs for
0
.16 mm, at 25 °C, pH 8.00, in DMSO/Tris·HCl buffer (1:1).
2b-Ln compared with those for 2c-Ln (Table 6).
The kinetic studies on the catalytic properties of the
To further study the effect of the HPNP concentration studied complexes suggest that the combination of different
on phosphodiester hydrolysis catalyzed by 2b-Ln and 2c- metal ions and types of ligands may enable the design of
Ln, kinetic data analyses were performed by using the highly efficient mimics of the hydrolytic enzyme.
Table 6. Kinetic data calculated for reactions of HPNP catalytic hydrolysis.
–
1
–1
–1 –1
Complex
k
obs [s ]
kobs/kuncat
k
cat [s ]
K
m
[mm]
M
kcat/K [s M ]
–4
–4
2
2
2
2
2
2
b-La
b-Eu
b-Lu
c-La
c-Eu
c-Lu
(7.44Ϯ0.18)ϫ10–6
(5.3Ϯ0.1)ϫ104
(1.08Ϯ0.04)ϫ10
(1.68Ϯ0.14)ϫ10
–
0.11Ϯ0.01
0.18Ϯ0.04
–
0.05Ϯ0.01
0.18Ϯ0.03
0.47Ϯ0.09
0.80Ϯ0.11
0.50Ϯ0.01
0.69Ϯ0.15
0.50Ϯ0.10
0.24Ϯ0.04
0.85Ϯ0.07
–
5
5
6
5
5
5
(2.35Ϯ0.38)ϫ10
(1.7Ϯ0.3)ϫ10
(3.36Ϯ0.12)ϫ10–
(6.16Ϯ0.53)ϫ10–
(2.4Ϯ0.1)ϫ105
(4.4Ϯ0.4)ϫ104
–5
–5
–4
(9.46Ϯ0.40)ϫ10
(9.39Ϯ0.50)ϫ10
(2.86Ϯ0.20)ϫ10
–
4
(1.07Ϯ0.09)ϫ10–
(7.6Ϯ0.6)ϫ10
(1.61Ϯ0.10)ϫ10
1,4ϫ10–
(1.2Ϯ0.1)ϫ105
10
no catalyst
1
Eur. J. Inorg. Chem. 2014, 3720–3730
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FULL PAPER
value.[51] Conversion from absorbance to concentration was per-
formed by using the Lambert–Beer law. Kinetic parameters (kcat
Conclusions
We have reported the synthesis and crystal studies of six and K ) were obtained by fitting the data to the Michaelis–Menten
M
new types of 3d–4f heterobinuclear complexes based on equation: [V
0 0 0 M 0 M
= kcat(complex) [S] /(K + [S] )], and kcat/K values
carbacylamidophosphates Cl CC(O)NHP(O)[N(Me) ] and were obtained by fitting the linear portion of the plot to V
0
= (kcat/
3
2 2
K
M
)[complex]
0 0
[S] .
Cl CC(O)NHP(O)[N(Et) ] and Schiff base ligand systems.
3
2 2
It was shown that the crystal structures of the complexes X-ray Structure Determination: Crystal data were collected with an
II
II
are composed of M(Ve) or M(Vp) (M = Zn , Ni ) moieties Xcalibur-3 diffractometer (graphite monochromated Mo-K radia-
α
and Ln-containing motifs forming together heterobinuclear tion, CCD detector, φ and ω-scanning). The structures were solved
molecules. For most of complexes, metal ions are connected
by two bridging phenolate oxygen atoms of (Ve) or (Vp)
[52]
by the direct method using the SHELXTL package. Full-matrix
2
2
–
least-squares refinement against F in anisotropic approximation
2
–
III
for non-hydrogen atoms was used. Positions of the hydrogen atoms
were located from electron density difference maps and refined by
the “riding” model with Uiso = nUeq of the carrier atom (n = 1.5
for methyl groups and n = 1.2 for other hydrogen atoms).
and an acetate group. The coordination number of Ln
II
and Zn ions is nine and five, respectively. In the case of
c-La, the NiII ion is tetracoordinated by two imine nitro-
gen atoms and two bridging phenolate oxygen atoms from
the (Ve) anion; the La center is ten-coordinated. In the
complex 2c-La, the Ni ion is six-coordinate, whereas the
1
2
–
III
CCDC-985564 (for 1a-La), -985565 (for 1b-Eu), -985566 (for 1c-
La), -985567 (for 2a-La), -985568 (for 2b-La), -985569 (for 2b-Eu),
and -985570 (for 2c-La) contain the supplementary crystallo-
graphic data for the paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
II
III
coordination number of La ion is nine. To the best of our
knowledge, the ability of the obtained 3d–4f complexes to
promote phosphodiester hydrolysis using the RNA mimic
substrate HPNP was demonstrated for the first time. The
kinetic data show that the rate of hydrolysis is linearly de-
pendent on complex concentration. Calculated rate con-
stants kobs for 2b-Ln and 2c-Ln follow the order
Lu Ͼ Eu Ͼ La, where 2b-Lu is the most effective, giving
five orders of magnitude improvement in the rate of the
catalyzed reaction compared with the noncatalyzed reac-
Syntheses
1
2
1
2
1
Synthesis of HL , HL , NaL , and NaL : Compounds HL and
2
HL were prepared and identified according to reported pro-
The sodium salts NaL and NaL were prepared by
reaction between equimolar amounts of sodium methylate and HL
cedures.[
30,31]
1
2
1
2
or HL in methanol medium and were used for preparation of com-
plexes without isolation from the reaction mixture. In the case of
Ni(Ve)-containing binuclear complexes, NaL were used in the
II
tion. The different ligand substitution mechanism for Ni
or Zn ions can presumably influence kobs values for the
2
II
same way, but obtained in 2-propanol medium starting from so-
dium isopropylate.
corresponding complexes.
II
II
Synthesis of H
2
Ve, H
2
Vp, M(Ve), and M(Vp) (M = Zn , Ni )
The Schiff bases H
2
Ve and H Vp were synthesized straightfor-
2
Experimental Section
wardly by condensation of 2-hydroxy-3-methoxybenzaldehyde and
the appropriate diamine (ethane-1,2-diamine or propane-1,3-di-
amine).[
Materials and Methods: All starting reagents used in this work were
obtained from commercial sources and used without further purifi-
cation. IR measurements were performed with a Perkin–Elmer
Spectrum BX spectrometer on samples in the form of KBr pellets.
NMR spectra were recorded with a Varian Mercury 400 NMR
53,54]
II
II
The complexes M(Ve) and M(Vp) (M = Zn , Ni ), were obtained
by reaction between methanol solution (2 mL) of zinc acetate
Zn(OAc)
0
0
2
·2H
.5 mmol) and a solution of H
.5 mmol] in chloroform (3 mL) and were used for the preparation
2
O (0.1097 g, 0.5 mmol) or Ni(OAc)
2 2
·4H O (0.1244 g,
1
31
spectrometer at 25 °C. H and P NMR spectra were recorded at
2
Ve (H Vp) [0.1642 g (0.1712 g),
2
4
00 and 162.1 MHz, respectively. Chemical shifts are reported with
1
31
4 3 4
reference to SiMe ( H) and H PO ( P). Elemental analyses (C,
of binuclear complexes without isolation in the individual state.
H, N) were performed with an EL III Universal CHNOS Elemen-
tal Analyzer. ESI MS were obtained with a Bruker APEX IV spec-
trometer. Predicted isotopic splitting patterns of peaks were calcu-
lated by using the program Isopro 3.1.
1a-La and 1b-Eu: Hydrated nitrate Ln(NO ·xH O (0.5 mmol) was
3
)
3
2
1
dissolved in methanol (2 mL) and mixed with NaL (1 mmol) in
methanol (3 mL). The mixture was added dropwise with constant
stirring to a hot solution of Zn(Ve) (0.5 mmol) and heated to reflux
for 1.5 h. The resulting solution was left in air at room temperature
and crystals of 1a-La and 1b-Eu, which formed after 7–9 days, were
filtered, washed with cold acetone and diethyl ether, and dried in
Kinetic Measurements: Kinetic measurements were recorded with a
Varian Cary 50 UV/Vis spectrophotometer at 25 °C, in 3 mL reac-
tion volumes using buffered solutions in DMSO/water (1:1); 2-
amino-2-hydroxymethylpropane-1,3-diol hydrochloride (Tris·HCl)
was used as a buffer. The reported results were obtained by averag-
ing of at least three independent measurements. In a typical experi-
ment, aqueous buffer solution (1.5 mL) was mixed with complex
stock solution (in DMSO, 0.5 mL) and DMSO (0.5 mL) in a tem-
perature-controlled spectrophotometric cell. After equilibration for
air. Yield: 60–75%. 1a-La: C32
calcd. C 32.55, H 3.84, N 9.49; found C 32.47, H 3.87, N 9.52. 1b-
Eu: C66 Zn (2451.61): calcd. C 32.33, H 4.03,
6 8 10 2
H45Cl LaN O P Zn (1180.71):
H
98Cl12Eu
2
N
16
O
22
P
4
2
N 9.14; found C 32.62, H 4.09, N 9.18.
3 3 2
1c-Ln, Ln = La, Nd: Hydrated nitrate Ln(NO ) ·xH O (0.5 mmol)
1
5
min, HPNP substrate stock solution (in DMSO, 0.5 mL) was
was dissolved in 2-propanol (2 mL) and mixed with NaL
(0.5 mmol) in 2-propanol (3 mL). The sodium nitrate was filtered
off and the resulting solution was added dropwise with constant
stirring to a hot solution of Ni(Ve) (0.5 mmol) and heated to reflux
for 3 h. The resulting light-orange precipitate was filtered off, dried
in air, and dissolved in a mixture of acetonitrile and chloroform
added and data collection was started immediately. The cleavage of
substrate was monitored by following the increase of the 4-nitro-
phenolate absorption at 405 nm. The activities of the complexes
were determined by the method of initial rates, taking into account
the molar absorptivity of the product at the corresponding pH
Eur. J. Inorg. Chem. 2014, 3720–3730
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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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(
5:1) upon heating. The solution was left to evaporate slowly in air
[5] C. Brewer, G. Brewer, W. R. Scheidt, M. Shang, E. E. Carpen-
ter, Inorg. Chim. Acta 2001, 313, 65–70.
at room temperature and crystals of 1c-La and a crystalline powder
of 1c-Nd, which were formed after 7–10 days, were filtered, washed
with cold acetone and diethyl ether, and dried in air. Yield: 50–
6
3
[
[
[
[
6] F. Pointillart, K. Bernot, Eur. J. Inorg. Chem. 2010, 952–964.
7] G. A. Brewer, E. Sinn, Inorg. Chem. 1987, 26, 1529–1535.
8] R. E. P. Winpenny, Chem. Soc. Rev. 1998, 27, 447–452.
9] J.-P. Costes, F. Dahan, A. Dupuis, J.-P. Laurent, New J. Chem.
0%. 1c-La: C24
H
30Cl
3
LaN
C
7
NiO12P (943.49): calcd. C 30.55, H
30.47, 3.25, 10.41. 1c-Nd:
.21,
N
10.39; found
H
N
1
998, 22, 1525–1529.
C
24
3 7
H30Cl N NdNiO12P (948.82): calcd. C 30.38, H 3.19, N 10.33;
[
10] M. Sasaki, K. Manseki, H. Horiuchi, M. Kumagai, M. Sakam-
oto, H. Sakiyama, Y. Nishida, M. Sakai, Y. Sadaoka, M. Ohba,
H. Okawa, J. Chem. Soc., Dalton Trans. 2000, 259–263.
found C 30.43, H 3.29, N 10.23.
2
a-Ln, Ln = La, Nd, Gd, Er: Prepared by following the procedure
[
11] M. Sakamoto, K. Manseki, H. Okawa, Coord. Chem. Rev.
2
described for 1a-Ln using HL as the staring ligand. Crystals of
2
7
2
001, 219–221, 379–414.
a-La and powders of 2a-Nd, 2a-Gd, and 2a-Er formed after 5–
[
[
12] C. Benelli, D. Gatteschi, Chem. Rev. 2002, 102, 2369–2387.
13] W. K. Lo, W.-K. Wong, J. Guo, W.-Y. Wong, K.-F. Li, K.-W.
Cheah, Inorg. Chim. Acta 2004, 357, 4510–4521.
days. Yield: 70–85%. 2a-La: C40 LaN Zn (1292.92):
H61Cl
6
8 10 2
O P
calcd. C 37.16, H 4.76, N 8.67; found C 37.28, H 4.69, N 8.71. 2a-
Nd: C40 NdO10 Zn (1298.26): calcd. C 37.01, H 4.74, N
.63; found 37.06, 4.78, 8.58. 2a-Gd:
GdN Zn (1311.27): calcd. C 36.64, H 4.69, N 8.55;
found C 36.57, H 4.66, N 8.51. 2a-Er: C40 ErN Zn
1321.28): calcd. C 36.36, H 4.65, N 8.48; found C 36.17, H 4.78,
N 8.52.
H61Cl
6
N
8
P
2
[14] W.-K. Lo, W.-K. Wong, W.-Y. Wong, J. Guo, K.-T. Yeung, Y.-
K. Cheng, X. Yang, R. A. Jones, Inorg. Chem. 2006, 45, 9315–
9325.
8
C
C
H
N
40
H61Cl
6
8 10 2
O P
[
[
[
15] C. E. Burrow, T. J. Burchell, P.-H. Lin, F. Habib, W.
H61Cl
6
8 10 2
O P
Wernsdorfer, R. Clerac, M. Murugesu, Inorg. Chem. 2009, 48,
(
8051–8053.
16] K. O. Znovjyak, O. V. Moroz, V. A. Ovchynnikov, T. Yu. Sliva,
S. V. Shishkina, V. M. Amirkhanov, Polyhedron 2009, 28, 3731–
3738.
2
b-Ln, Ln = La, Nd, Eu, Dy, Er, Lu: Prepared by following the
2
2–
procedure described for compounds 1a-Ln using HL and (Vp)
as the staring ligands. Crystals of 2b-La, 2b-Eu, and powders of
17] N. S. Kariaka, V. A. Trush, V. V. Medviediev, T. Y. Sliva, V. M.
Amirkhanov, Acta Crystallogr., Sect. E. 2013, 69, m143.
18] D. E. Wilcox, Chem. Rev. 1996, 96, 2435–2458.
19] R Mitra, M. W. Peters, M. J. Scott, Dalton Trans. 2007, 35,
2
8
4
b-Nd, 2b-Dy, 2b-Er, and 2b-Lu formed after 5–7 days. Yield: 70–
0%. 2b-La: C41 LaN Zn (1306.95): calcd. C 37.68, H
8.57; found 37.55, 4.90, 8.50. 2b-Nd:
NdO10 Zn (1312.28): calcd. C 37.53, H 4.84, N 8.54;
EuN Zn
1320.00): calcd. C 37.31, H 4.81, N 8.49; found C 37.27, H 4.78,
N 8.47. 2b-Dy: C41 DyN Zn (1330.54): calcd. C 37.01,
[
[
H63Cl
6
8 10 2
O P
.86,
N
C
H
N
3924–3935.
C
41
H63Cl
6
N
8
P
2
[
20] R. A. Mathews, C. S. Rossiter, J. R. Morrow, J. P. Richard, Dal-
ton Trans. 2007, 34, 3804–3811.
21] N. H. Williams, B. Takasaki, M. Wall, J. Chin, Acc. Chem. Res.
1999, 32, 485–493.
found C 37.48, H 4.82, N 8.49. 2b-Eu: C41
(
H63Cl
6
8 10 2
O P
[
H63Cl
6
8 10 2
O P
H 4.77, N 8.42; found C 36.89, H 4.80, N 8.39. 2b-Er: [22] L. Bonfa, M. Gatos, F. Mancin, P. Tecilla, U. Tonellato, Inorg.
C
41
H
63Cl
found C 36.65, H 4.74, N 8.25. 2b-Lu: C41
1343.01): calcd. C 36.67, H 4.73, N 8.34; found C 36.63, H 4.73,
N 8.29.
6
ErN
8
O
10
P
2
Zn (1335.30): calcd. C 36.88, H 4.76, N 8.39;
Chem. 2003, 42, 3943–3949.
[
[
23] B. K. Takasaki, J. Chin, J. Am. Chem. Soc. 1993, 115, 9337–
H63Cl
6
8 10 2
LuN O P Zn
9338.
(
24] B. K. Takasaki, J. Chin, J. Am. Chem. Soc. 1995, 117, 8582–
8585.
2
c-Ln, Ln = La, Eu, Gd, Er, Lu: Hydrated nitrate Ln(NO
3
)
3
·xH
2
O
[25] R. Breslow, B. Zhang, J. Am. Chem. Soc. 1994, 116, 7893–7894.
[26] J. Kamitani, J. Sumaoka, H. Asanuma, M. Komiyama, J.
Chem. Soc. Perkin Trans. 2 1998, 523–528.
2
(
(
0.5 mmol) was dissolved in methanol (2 mL) and mixed with NaL
1 mmol) in methanol (3 mL). The resulting solution was added
[27] V. V. Skopenko, V. M. Amirkhanov, T. Yu. Sliva, I. S. Vasilch-
dropwise with constant stirring to a hot solution of Ni(Vp)
0.5 mmol) and heated to reflux for 1 h. The reaction mixture was
enko, E. L. Anpilova, A. D. Garnovskii, Usp. Khim. 2004, 73,
(
7
97–813.
left in air at room temperature, and crystals of 2c-La and powders
of 2c-Eu, 2c-Gd, 2c-Er, and 2c-Lu formed after 3–5 days. Yield:
[
[
28] O. O. Litsis, V. A. Ovchynnikov, S. V. Shishkina, T. Y. Sliva,
V. M. Amirkhanov, Trans. Met. Chem. 2013, 38, 473–479.
29] K. O. Znovjyak, V. A. Ovchynnikov, T. Yu. Sliva, S. V. Shish-
kina, V. M. Amirkhanov, Acta Crystallogr., Sect. E. 2010, 66,
m306.
7
5–85%. 2c-La: C42
H 5.07, N 8.41; found C 37.68, H 5.09, N 8.44. 2c-Eu:
EuN NiO11 (1345.37): calcd. C 37.50, H 5.02, N 8.33;
found C 37.53, H 5.05, N 8.36. 2c-Gd: C42 GdN NiO11
1350.66): calcd. C 37.35, H 5.00, N 8.30; found C 37.28, H 4.91,
N 8.11. 2c-Er: C42 ErN NiO11 (1360.67): calcd. C 37.07,
H 4.96, N 8.24; found C 37.12, H 5.08, N 8.19. 2c-Lu:
LuN NiO11 (1368.38): calcd. C 36.87, H 4.94, N 8.19;
6 8 2
H67Cl LaN NiO11P (1332.32): calcd. C 37.86,
C
42
H67Cl
6
8
P
2
H67Cl
6
8
P
2
[30] O. V. Amirkhanov, O. V. Moroz, K. O. Znovjyak, E. A. Trush,
(
T. Yu. Sliva, Acta Crystallogr., Sect. E. 2010, 66, O1102.
[
[
[
31] V. M. Amirkhanov, V. A. Ovchynnikov, V. A. Trush, V. V. Skop-
H67Cl
6
8
P
2
enko, Zh. Org. Khim. 1996, 32, 376–380.
32] W.-K. Wong, H. Liang, W.-Y. Wong, Z. Cai, K.-F. Li, K.-W.
Cheah, New J. Chem. 2002, 26, 275–278.
33] X.-P. Yang, R. A. Jones, Q.-Y. Wu, M. M. Oye, W.-K. Lo, W.-
K. Wong, A. L. Holmes, Polyhedron 2006, 25, 271–278.
[34] J.-P. Costes, G. Novitchi, S. Shova, F. Dahan, B. Donnadieu,
C
42
H67Cl
6
8
P
2
found C 36.80, H 4.96, N 8.20.
Supporting Information (see footnote on the first page of this arti-
cle): IR, H and P NMR spectral details of the synthesized com-
pounds, molecular structures of 2a-La and 2b-Eu, and MS data for
2
1
31
J.-P. Tuchagues, Inorg. Chem. 2004, 43, 7792–7799.
[
35] G. Novitchi, S. Shova, A. Caneschi, J.-P. Costes, M. Gdaniec,
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5–7.
b-Nd, 2c-La, and 2c-Er.
[
[
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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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Received: March 25, 2014
Published Online: July 10, 2014
2
Eur. J. Inorg. Chem. 2014, 3720–3730
3730
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim