Synthesis and structural features of new ruthenium(ii) complexes containing the scorpionate ligands tris(pyrazol-1-yl)methanesulfonate (Tpms) and tris(pyrazol-1-yl)methane (Tpm)

Article abstract of DOI:10.1002/ejic.201100621

New ruthenium(II) scorpionate complexes containing tris(pyrazol-1-yl) methanesulfonate (Tpms) and tris(pyrazol-1-yl)methane (Tpm) ligands have been synthesized. For complexes with Tpms, two isomers are obtained as the kinetic (1a) and thermodynamic (1b) p

Full text of DOI:10.1002/ejic.201100621

FULL PAPER
DOI: 10.1002/ejic.201100621
Synthesis and Structural Features of New Ruthenium(II) Complexes
Containing the Scorpionate Ligands Tris(pyrazol-1-yl)methanesulfonate (Tpms)
and Tris(pyrazol-1-yl)methane (Tpm)
Sara Miguel,[a] Josefina Diez,[a] Ma Pilar Gamasa,[a] and Ma Elena Lastra*[a]
Keywords: Ruthenium / Scorpionate ligands / Phosphane ligands / N,O ligands
New ruthenium(II) scorpionate complexes containing tris-
(pyrazol-1-yl)methanesulfonate (Tpms) and tris(pyrazol-1-yl)-
Tpms ligand is favored over κ3(N,N,O) coordination. In ad-
dition, complexes with water soluble phosphane ligands
methane (Tpm) ligands have been synthesized. For com- 1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane (PTA) and 1-
plexes with Tpms, two isomers are obtained as the kinetic
(1a) and thermodynamic (1b) products, which shows that, for
these complexes, the κ3(N,N,N) coordination mode of the
alkyl-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.13,7]decane
(1-R-PTA) have been prepared and structurally charac-
terized.
unit is a weakly coordinating group, especially in compari-
son with nitrogen atom donors. Moreover, κ2(N,N) coordi-
nation of Tpms has been described for rhodium(I) com-
plexes[7] and proposed for iridium(I) catalysts.[8]
Introduction
Scorpionate ligands have been widely used in coordina-
tion chemistry due to the rich chemistry of their metal com-
plexes, which have been extensively used in stoichiometric
and catalytic chemistry. In particular, complexes bearing the
anionic tris(pyrazol-1-yl)borate (Tp) ligand have been
prominently studied.[1] However, the chemistry of transition
metal complexes bearing other trispyrazolyl ligands has
been far less developed.
For instance, tris(pyrazolyl)alkanes, such as tris(pyrazol-
1-yl)methane (Tpm), constitute a family of stable and flexi-
ble polydentate ligands isoelectronic and isosteric with tris-
(pyrazolyl)borates, the major difference being the charge.[2]
Replacement of the methyne proton in Tpm by a methane-
sulfonate unit[3] leads to the tris(pyrazol-1-yl)methanesulf-
onate ligand (Tpms). This ligand constitutes a versatile al-
ternative to tris(pyrazolyl)borate, as the sulfonate group is
noninnocent and plays a determining role on the properties
of the complexes, for example by imparting hydrosolubility.
In addition, the oxygen atom from the sulfonate unit may
coordinate with the metal atoms. Thus, for this ligand,
apart from the tripodal κ3(N,N,N) coordination mode,[4]
κ3(N,N,O) coordination has been described for several
metal complexes,[5] which can be used as models for N,N,O
binding in metalloenzymes,[6] regardless that the sulfonate
This versatile behavior of the Tpms ligand and the in-
creased water solubility of its complexes compared to Tp
complexes, prompted us to explore the chemistry of ruthe-
nium complexes as, to the best of our knowledge, no ruthe-
nium complexes have been synthesized with this ligand.
We have recently reported the synthesis and antitumor
activity of a series of ruthenium(II) complexes containing
tris(pyrazol-1-yl)borate.[9] In this article, we report the syn-
thesis and structural features of ruthenium(II) complexes
bearing the scorpionate ligand Tpms (Figure 1). Further-
more, our interest in water soluble complexes, which could
be used in biological assays, prompted us to study phos-
phane substitution with the water soluble 1,3,5-triaza-7-
phosphatricyclo[3.3.1.13,7]decane (PTA) phosphane as well
as electrophilic attacks on coordinated PTA phosphanes
yielding new ruthenium(II) complexes. Synthesis and reac-
tivity studies of the cationic complex [RuCl{κ3(N,N,N)-
Tpm}(PPh3)(PTA)]Cl, bearing neutral Tpm, are also de-
scribed.
[a] Departamento de Química Orgánica e Inorgánica, Instituto de
Química Organometálica “Enrique Moles” (Unidad Asociada
al C.S.I.C.), Universidad de Oviedo,
33006 Oviedo, Principado de Asturias, Spain
Fax: +34-985103446
E-mail: elb@uniovi.es
Figure 1. Tpm and Tpms ligands.
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S. Miguel, J. Diez, M. P. Gamasa, M. E. Lastra
FULL PAPER
phanes as two doublets at 8.91 and 6.99 ppm (3-H and 5-
H) and a triplet at 5.85 ppm (4-H) and the hydrogen atoms
for the ring trans to the chloride as two doublets at 9.10
and 5.21 ppm (3-H and 5-H) and a triplet at 5.42 ppm (4-
H). For 1b the hydrogen atoms of the pyrazole rings trans
to the phosphanes appear as two doublets at 6.99 and 6.97
ppm (3-H and 5-H) and a triplet at 5.79 ppm (4-H). The
hydrogen atoms for the noncoordinated pyrazole ring ap-
pear at lower field as two doublets at 9.00 and 7.90 ppm (3-
H and 5-H) and a triplet at 6.60 ppm (4-H), and
(iii) 13C{1H} NMR spectra show the expected signals for
the two complexes. In all cases the assignment of the signals
has been confirmed by 2D COSY, heteronuclear single
quantum coherence (HSQC), and HMBC NMR experi-
ments.
In order to determine the structural differences between
1a and 1b, X-ray diffraction studies were carried out. Slow
diffusion of hexane into a solution of 1a in dichlorometh-
ane or 1b in tetrahydrofuran (THF), resulted in crystals of
1a·CH2Cl2 and 1b·THF suitable for X-ray diffraction stud-
ies. An ORTEP view of the molecules is shown in Figure 2,
and selected bond lengths and angles are presented in
Table 1.
Results and Discussion
Ruthenium(II) Complexes Containing κ3(N,N,N)- and
κ3(N,N,O)-Tpms. Synthesis of [RuCl{κ3(N,N,N)-
Tpms}(PPh3)2] (1a) and [RuCl{κ3(N,N,O)-Tpms}(PPh3)2]
(1b)
The reaction of one equivalent of the lithium salt of
Tpms with [RuCl2(PPh3)3] in hot methanol gave
[RuCl{κ3(N,N,N)-Tpms}(PPh3)2] (1a), which was isolated
as a yellow solid in 95% yield. When this reaction was car-
ried out in a 1:10 CH2Cl2/MeOH mixture at 0 °C,
[RuCl{κ3(N,N,O)-Tpms}(PPh3)2] (1b) was isolated as an
orange solid in 57% yield. When complex 1b was heated in
CH2Cl2, isomerization to 1a was observed (Scheme 1),
which indicates that 1a is the thermodynamically stable
product. Complete transformation can also be observed at
room temperature within a few days.
Scheme 1.
1
Spectroscopic data (IR and H, 13C{1H}, and 31P{1H}
NMR spectroscopy) support the proposed formulation. In
particular, IR spectra are especially informative as they al-
low the establishment of the coordination mode of Tpms in
the complexes. Thus, for 1a the IR spectrum shows two me-
Figure 2. Molecular structure and atom labeling scheme for
1a·CH2Cl2 and 1b·THF. Solvent molecules and hydrogen atoms
have been omitted for clarity. Non-hydrogen atoms are represented
dium signals at 1286 and 1054 cm–1 due to the S–O bond by 50% probability ellipsoids.
and a weak band at 832 cm–1 due to the C–N bond of the
pyrazole rings. However, for 1b, the IR spectrum shows
In both complexes, the ruthenium ion exhibits a distorted
more bands in the region 1400–1000 cm–1 than for 1a, and octahedral coordination geometry bonded to one chlorine
two different bands at 1088 and 860 cm–1 for the C–N atom, two phosphorus atoms of the PPh3 ligands, and the
bonds can be observed, which indicate κ3(N,N,O) coordina- Tpms ligand, which shows κ3(N,N,N) coordination for 1a
tion for Tpms.[10] In both complexes, the band due to the and κ3(N,N,O) coordination for 1b. In 1b, the chlorine atom
C–S stretching vibration appears at 621 cm–1.
is located trans to the oxygen atom and the third pyrazolyl
The rest of the data are in accordance with the proposed ring acts a pendant uncoordinated pyrazolate group.
structures: (i) a singlet resonance is observed at 38.9 (1a) κ3(N,N,O) coordination for Tpms has been described for
and 35.8 (1b) ppm in the 31P{1H} NMR spectra indicating several metal complexes.[5,6] Studies carried out with steri-
the equivalence of the two phosphorus atoms for both com- cally hindered substituted Tpms point out that the ligand
plexes. For complex 1b, this involves the oxygen atom from tends to adapt its coordination mode to suit the electronic
the methanesulfonate unit trans to the chlorine atom, and steric preferences of the metal center.[11]
1
(ii) the H NMR spectrum of 1a shows the signals for the
The N–Ru–N angles and Ru–N bond lengths for both
hydrogen atoms of the pyrazole rings trans to the phos- complexes are in the range found for hydridotris(pyrazolyl)-
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New Ruthenium(II) Complexes Containing Scorpionate Ligands
Table 1. Selected bond lengths [Å] and angles [°] for 1a·CH2Cl2 and 1a occurs under the reaction conditions. In the same way,
treatment of the analogous complex [RuCl{κ3(N,N,N)-
1b·THF.
Tpm}(PPh3)2]Cl[13] with one equivalent of PTA in hot tolu-
Selected bond lengths for 1a·CH2Cl2
ene led to 4 as a yellow air-stable solid in 79% yield
(Scheme 2).
Ru(1)–N(1)
Ru(1)–N(3)
Ru(1)–N(5)
2.128(2)
2.104(2)
2.068(2)
Ru(1)–P(1)
Ru(1)–P(2)
Ru(1)–Cl(1)
2.4002(7)
2.3607(7)
2.4060(7)
Selected bond angles for 1a·CH2Cl2
N(1)–Ru(1)–N(3) 79.07(9)
N(1)–Ru(1)–N(5) 84.10(9)
N(3)–Ru(1)–N(5) 87.06(10)
N(1)–Ru(1)–P(1) 166.29(7)
N(1)–Ru(1)–P(2) 91.66(6)
N(3)–Ru(1)–P(1) 88.92(7)
N(3)–Ru(1)–P(2) 169.68(7)
N(5)–Ru(1)–P(1)
N(5)–Ru(1)–P(2)
N(1)–Ru(1)–Cl(1) 88.81(7)
N(3)–Ru(1)–Cl(1) 86.92(7)
N(5)–Ru(1)–Cl(1) 171.46(7)
P(1)–Ru(1)–P(2)
P(1)–Ru(1)–Cl(1) 97.22(3)
P(2)–Ru(1)–Cl(1) 88.37(3)
88.73(7)
96.56(6)
100.78(2)
Selected bond lengths for 1b·THF
Ru(1)–N(1)
Ru(1)–N(3)
Ru(1)–O(3)
2.135(5)
2.128(4)
2.131(4)
Ru(1)–P(1)
Ru(1)–P(2)
Ru(1)–Cl(1)
2.3683(17)
2.3544(13)
2.3917(15)
Selected bond angles for 1b·THF
N(1)–Ru(1)–N(3) 77.15(18)
N(1)–Ru(1)–O(3) 90.40(18)
N(3)–Ru(1)–O(3) 83.64(15)
N(1)–Ru(1)–P(1) 169.26(12)
N(1)–Ru(1)–P(2) 93.47(12)
O(3)–Ru(1)–P(1) 86.63(12)
O(3)–Ru(1)–P(2) 92.43(10)
N(3)–Ru(1)–P(1)
N(3)–Ru(1)–P(2)
N(1)–Ru(1)–Cl(1) 83.25(14)
N(3)–Ru(1)–Cl(1) 87.92(12)
O(3)–Ru(1)–Cl(1) 170.40(11)
P(1)–Ru(1)–P(2)
P(1)–Ru(1)–Cl(1) 98.29(6)
P(2)–Ru(1)–Cl(1) 95.12(5)
92.25(14)
169.76(13)
Scheme 2.
Complexes 2, 3, and 4 are soluble in common organic
solvents such as methanol, chloroform, and dichlorometh-
ane and insoluble in diethyl ether and hexane. In spite of
the presence of the sulfonate group and PTA unit, 3 is insol-
uble in water, and 2 is only slightly soluble in water
(1.8 mgmL–1). Surprisingly, 4 shows higher water solubility
(2.8 mgmL–1) than 2 and 3, even though Tpm is supposed
to induce lower water solubility than Tpms. The molar con-
ductivity in nitromethane for 4 (76 Scm2 mol–1) agrees with
a 1:1 electrolyte.[14] The complexes have been analytically
96.97(5)
borate ruthenium(II) complexes. N–Ru–N bond angles for
1a·CH2Cl2 (79.07–87.06°) are larger than that for 1b
(77.16°) and close to the N–Ru–O bond angles (83.65–
90.29°). For 1a, the shortest Ru–N bond length corresponds
to Ru(1)–N(5) [2.068(2) Å], which is trans to the chlorine
atom, in accordance with the higher trans influence of the
phosphane ligands.[12]
and spectroscopically characterized (IR and H, 13C{1H},
1
and 31P{1H} NMR spectroscopy). In particular, it should
be noted that: (i) the IR spectra (KBr) show the characteris-
tic ν(C–S) absorption for Tpms at 621 (2) and 622 cm–1 (3),
(ii) the 31P{1H} spectrum exhibits a singlet at –33.1 ppm for
2 and two doublet resonances at 43.5 and –37.9 ppm (JP,P
= 34 Hz) and 44.9 and –35.1 ppm (JP,P = 36 Hz) for the
PPh3 and the PTA ligands of 3 and 4, respectively, (iii) the
Complexes with PTA – Synthesis of [RuCl{κ3(N,N,N)-
Tpms}(PTA)2] (2), [RuCl{κ3(N,N,N)-Tpms}(PPh3)(PTA)]
(3), and [RuCl{κ3(N,N,N)-Tpm}(PPh3)(PTA)][Cl] (4)
Complex 1a underwent phosphane substitution with 1H NMR spectrum of 2 in CDCl3 shows the signals for the
PTA under different reaction conditions, which led to hydrogen atoms of the pyrazole rings trans to the phos-
[RuCl{κ3(N,N,N)-Tpms}(PTA)2] (2) and [RuCl{κ3(N,N,N)- phanes as two doublets at 9.05 and 8.07 ppm (3-H and 5-
Tpms}(PPh3)(PTA)] (3). In order to establish a comparison H) and a triplet at 6.45 ppm (4-H), and the hydrogen atoms
between complexes with Tpms and Tpm, analogous for the ring trans to the chloride as two doublets at 9.24
[RuCl{κ3(N,N,N)-Tpm}(PPh3)(PTA)][Cl] (4) was synthe- and 7.19 ppm (3-H and 5-H) and a triplet at 6.43 ppm (4-
sized.
H). For 3 the hydrogen atoms of the pyrazole rings are in-
Thus, heating concentrated toluene solutions of 1a and equivalent and appear as doublets and triplets in the range
1
PTA in a ratio 1:2.3 produced 2, which precipitated from 9.10–5.88. The H NMR spectra also show the signals for
the reaction mixture and was isolated as a yellow solid in the PTA ligands as AB spin systems of the NCH2N group
85% yield. When the same reaction was carried out using at 4.60 and 4.48 ppm (JHA,HB = 13 Hz) for 2 and at 4.45
a stoichiometric amount of PTA and more diluted solutions and 4.26 ppm (JHA,HB = 13 Hz) for 3. The NCH2P protons
in hot toluene, 3 was isolated as an air-stable yellow solid appear as a singlet at 4.18 ppm in 2 and 3.91 ppm in 3,
in 79% yield (Scheme 2). Moreover, 3 reacts with an excess (iv) 13C{1H} NMR spectra reveal the CH2 groups of the
of PTA, giving rise to 2 (Scheme 2). The corresponding PTA ligand as doublets at 73.3 (3JC,P = 6 Hz) (NCH2N)
complexes with Tpms coordinated in a κ3(N,N,O) fashion and 53.3 ppm (JC,P = 15 Hz) (NCH2P) for 2 and at 73.2
could not be synthesized as fast isomerization from 1b to (3JC,P = 6 Hz) (NCH2N) and 51.6 ppm (JC,P = 14 Hz)
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S. Miguel, J. Diez, M. P. Gamasa, M. E. Lastra
FULL PAPER
(NCH2P) for 3. For both complexes, the signals for the pyr- tion studies. ORTEP representations are shown in Figure 3,
azole rings appear in the range 148.2–106.6 ppm, and and selected bond lengths and angles are presented in
(iv) 1H NMR spectra are especially informative for Tpm Table 2.
complexes due to the methane Tpm proton, which appears
For both complexes, the ruthenium ion exhibits a dis-
at low field (12.24 ppm for 4) separated from the rest of the torted octahedral coordination geometry bonded to one
proton resonances of the pyrazole rings in the range 8.87– chlorine atom, two phosphorus atoms of the phosphane li-
5.86 ppm and those for the PTA phosphane, which appears gands, and the nitrogen atoms of Tpms. The N–Ru–N
as AB spin systems at 4.45 and 4.26 ppm (NCH2N) and angles and Ru–N bond lengths for both complexes are in
3.96 and 3.89 ppm (NCH2P). The signals in the 13C{1H} the range found for hydridotris(pyrazolyl)borate rutheni-
NMR spectra have been fully assigned and agree with the um(II) complexes,[9] and the small N–Ru–N angles (80.01–
proposed complexes (see Exp. Sect.).
86.04°) reflect the fac environment of the ligand around the
Slow evaporation of a water solution of 2, and slow dif- ruthenium ion. The P–Ru–P angle in 3 [97.18(3)°] is signifi-
fusion of hexane into an acetone solution of 3 resulted in cantly larger than that in 2 [93.337(16)°] as a consequence
crystals of 2·4H2O and 3·2C3H6O suitable for X-ray diffrac- of the steric bulk of the PPh3 ligand.
Electrophilic Attack on PTA Complexes
As we have reported previously,[15] complexes containing
PTA ligands undergo electrophilic attack at the coordinated
PTA yielding new complexes containing modified PTA
phosphanes. Thus, 1a reacts with different electrophiles to
yield N-substituted derivatives.
Synthesis of [RuCl{κ3(N,N,N)-Tpms}(PPh3)(1-H-PTA)][X]
[X = BF4 (5a), Cl (5b)] and [RuCl{κ3(N,N,N)-Tpm}(PPh3)-
(1-H-PTA)][X]2 [X = BF4 (6a), Cl (6b)]
Figure 3. Molecular structure and atom labeling scheme for
2·4H2O and 3·2C3H6O. Solvent molecules and hydrogen atoms
Addition of an equimolecular amount of HBF4 to a
have been omitted for clarity. Non-hydrogen atoms are represented
solution of 3 in dichloromethane at –30 °C produced
by 50% probability ellipsoids.
[RuCl{κ3(N,N,N)-Tpms}(PPh3)(1-H-PTA)][BF4]
(5a),
which precipitated upon addition of diethyl ether. In the
same way, addition at –30 °C of an equimolecular amount
of HBF4 to
Table 2. Selected bond lengths [Å] and angles [°] for 2·CH2Cl2 and
3·2C3H6O.
a
solution of [RuCl{κ3(N,N,N)-Tpm}-
Selected bond lengths for 2·CH2Cl2
(PPh3)(PTA)][BF4], generated in situ from 4 and NaBF4,
allows the isolation of [RuCl{κ3(N,N,N)-Tpm}(PPh3)(1-H-
PTA)][BF4]2 (6a) as a yellow solid in 80% yield. The forma-
tion of 5a and 6a comes from the protonation of one nitro-
gen atom of the coordinated PTA ligand leading to the 3,5-
diaza-1-azonia-7-phosphatricyclo[3.3.1.13,7]decane ligand
(1-H-PTA, Scheme 3). Complexes [RuCl{κ3(N,N,N)-
Tpms}(PPh3)(1-H-PTA)][Cl] (5b) and [RuCl{κ3(N,N,N)-
Tpm}(PPh3)(1-H-PTA)][Cl]2 (6b) were obtained by treat-
ment of 3 and 4 in dichloromethane with a 2 n solution of
HCl in diethyl ether at 0 °C. Elemental analyses and NMR
Ru(1)–N(1)
Ru(1)–N(3)
Ru(1)–N(5)
2.1252(14) Ru(1)–P(1)
2.0639(14) Ru(1)–P(2)
2.1248(14) Ru(1)–Cl(1)
2.2937(4)
2.2859(4)
2.4105(4)
Selected bond angles for 2·CH2Cl2
N(1)–Ru(1)–N(3)
N(1)–Ru(1)–N(5)
N(3)–Ru(1)–N(5)
N(1)–Ru(1)–P(1)
N(1)–Ru(1)–P(2)
N(3)–Ru(1)–P(1)
N(3)–Ru(1)–P(2)
N(5)–Ru(1)–P(1)
84.26(6)
81.06(6)
84.89(6)
175.48(4)
90.65(4)
97.59(4)
93.66(4)
94.97(4)
N(5)–Ru(1)–P(2)
171.68(4)
N(1)–Ru(1)–Cl(1) 88.69(4)
N(3)–Ru(1)–Cl(1) 171.21(4)
N(5)–Ru(1)–Cl(1) 88.83(4)
P(1)–Ru(1)–Cl(1)
P(2)–Ru(1)–Cl(1)
P(1)–Ru(1)–P(2)
89.073(16)
91.665(16)
93.337(16)
Selected bond lengths for 3·2C3H6O
Ru(1)–N(1)
Ru(1)–N(3)
Ru(1)–N(5)
2.145(3)
2.129(3)
2.071 (3)
Ru(1)–P(1)
Ru(1)–P(2)
Ru(1)–Cl(1)
2.2971(8)
2.3242(9)
2.4155(9)
Selected bond angles for 3·2C3H6O
N(1)–Ru(1)–N(3)
N(1)–Ru(1)–N(5)
N(3)–Ru(1)–N(5)
N(1)–Ru(1)–P(1)
N(1)–Ru(1)–P(2)
N(3)–Ru(1)–P(1)
N(3)–Ru(1)–P(2)
N(5)–Ru(1)–P(1)
80.01(11)
86.04(12)
84.63(11)
168.73(8)
93.52(8)
89.31(8)
173.50(8)
89.43(9)
N(5)–Ru(1)–P(2)
95.57(8)
N(1)–Ru(1)–Cl(1) 90.16(8)
N(3)–Ru(1)–Cl(1) 87.93(10)
N(5)–Ru(1)–Cl(1) 86.41(8)
P(1)–Ru(1)–Cl(1)
P(2)–Ru(1)–Cl(1)
P(1)–Ru(1)–P(2)
92.76(4)
93.07(3)
97.18(3)
Scheme 3.
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New Ruthenium(II) Complexes Containing Scorpionate Ligands
spectroscopic data support the proposed formulations.
However, conductivity measurements in nitromethane indi-
cate some differences since the conductivity values for 5b
(65 Scm2 mol–1) and 6b (67 Scm2 mol–1) are significantly
lower than expected for a 1:1 electrolyte (75–95 Scm2 mol–1)
and 1:2 electrolyte (150–180 Scm2 mol–1),[14] whereas the
values found for 5a (83 Scm2 mol–1) and 6a (182
Scm2 mol–1) agree with those expected. An explanation for
the low values observed for 5b and 6b can be found in the
formation of an ionic pair between the proton bonded to
the nitrogen atom of the 1-H-PTA ligand and the chlorine
counteranion. Unfortunately, this proton could not be iden-
1
tified in the H NMR spectra of these complexes.
The relevant spectroscopic parameters for 5a and 6a are
similar to those of 5b and 6b except for the 31P{1H} NMR
spectra, which are quite different. Thus, the 31P{1H} spectra
exhibit two doublets at 39.9 and –19.6 ppm (2JPP = 34 Hz)
for 5a and 39.6 and –23.4 ppm (2JPP = 33 Hz) for 5b for
PPh3 and 1-H-PTA, respectively. In addition, the signals
corresponding to the 1-H-PTA ligand for 6a and 6b are
quite different: –24.2 ppm (2JPP = 34 Hz) for 6a and
–20.7 ppm (2JPP = 34 Hz) for 6b. In all cases, the signal for
the 1-H-PTA is clearly shifted to a lower field compared to
the value found in 3 (–37.9 ppm) as previously reported for
Figure 4. Molecular structure and atom labeling scheme for the
complex cations of 5a·2NCMe and 6b. Solvent molecules and hy-
drogen atoms, except N–H, and the apical hydrogen atom of Tpm
are omitted for clarity. Non-hydrogen atoms are represented by
50% probability ellipsoids.
Table 3. Selected bond lengths [Å] and angles [°] for 5a·2NCMe
and 6b.
Selected bond lengths for 5a·2NCMe
Ru(1)–N(1)
2.145(2)
2.071(2)
2.120(2)
2.2937(7)
2.3199(6)
Ru(1)–Cl(1)
C(11)–N(7)
C(14)–N(7)
C(15)–N(7)
N(7)–H(1)
2.4146(6)
1.498(3)
1.531(4)
1.527(3)
1.06(5)
N-protonated PTA.[15] The differences in the chemical shift Ru(1)–N(3)
Ru(1)–N(5)
could be due to a weak hydrogen bonding interaction with
Ru(1)–P(1)
the chlorine anion in 5b and 6b, which would agree with
Ru(1)–P(2)
the low conductivity values. For the rest of the spectro-
Selected bond angles for 5a·2NCMe
scopic data, only the data corresponding to 5a and 6a will
be discussed. Thus, for 5a the IR spectrum (KBr) shows the
characteristic ν(C–S) absorption for Tpms at 622 cm–1 and
N(1)–Ru(1)–N(3)
N(1)–Ru(1)–N(5)
N(3)–Ru(1)–N(5)
86.25(9)
79.70(9)
83.80(8)
P(1)–Ru(1)–Cl(1) 91.23(2)
P(2)–Ru(1)–Cl(1) 92.44(2)
P(1)–Ru(1)–P(2) 96.13(2)
1
the ν(B–F) absorption at 1031 cm–1. The H NMR spec-
Selected bond lengths for 6b
trum shows the expected AB systems for the hydrogen
atoms of the NCH2N and NCH2P groups of PTA at 4.67 Ru(1)–N(1)
2.128(7)
2.159(6)
2.078 (6)
2.280(2)
2.326(2)
2.10
Ru(1)–Cl(1)
C(11)–N(7)
C(14)–N(7)
C(16)–N(7)
N(7)–H(7N)
N(7)H–Cl
2.409(2)
1.505(11)
1.570(12)
1.511(12)
1.06(5)
Ru(1)–N(3)
and 4.49 ppm (JHAHB = 12 Hz) for 5a, 4.59 and 4.47 ppm
Ru(1)–N(5)
(JHAHB = 12 Hz) for 6a, and 3.91 and 3.45 ppm (JHCHD
=
Ru(1)–P(1)
Ru(1)–P(2)
H(7N)–Cl(3)
13 Hz) for 5a, and 3.87 ppm for 6a, respectively. The
13C{1H} NMR spectrum reveals the CH2 groups of PTA
as doublet signals at 71.5 (3JCP = 6 Hz) (NCH2N) and 48.1
ppm (JCP = 14 Hz) (NCH2P) for 5a and two singlets at 71.3
(NCH2N) and 49.1 ppm (NCH2P) for 6a. The signals for
the carbon atoms of the pyrazole rings appear in the range
2.9769
Selected bond angles for 6b
N(1)–Ru(1)–N(3)
N(1)–Ru(1)–N(5)
N(3)–Ru(1)–N(5)
81.4(3)
84.8(3)
86.6(2)
P(1)–Ru(1)–Cl(1) 91.60(7)
P(2)–Ru(1)–Cl(1) 93.75(8)
P(1)–Ru(1)–P(2) 97.04(8)
149.8–106.9 ppm. The signal for the apical CSO3 carbon N(7)–H(7N)–Cl(3) 171
atom for 5a appears at 90.6 ppm.
Slow evaporation of NCMe solutions of 5a and 6b gave
crystals suitable for X-ray diffraction studies. ORTEP repre- bond lengths trans to the phosphane ligands [2.145(2) and
sentations of the complex cations are shown in Figure 4, 2.120(2) Å] are significantly longer those trans to the chlo-
and selected bond lengths and angles are collected in rine atom [Ru(1)–N(3) = 2.071(2) Å], which is in accord-
Table 3.
ance with the higher trans influence for the phosphane li-
In both complexes, the ruthenium ion exhibits a distorted gands.[12]
octahedral coordination geometry bonded to one chlorine
The most important feature for these complexes is the
atom, two phosphorus atoms of the phosphane ligands, and hydrogen bonding between the NH and the Cl–
the nitrogen atoms of κ3(N,N,N)-Tpms for 5a and Tpm for counteranion found in 6b (Figure 5). This N–H–Cl interac-
6b. The N–Ru–N angles and Ru–N bond lengths for both tion can be demonstrated by the short H···Cl (2.10 Å) and
complexes are in the range found for hydridotris(pyrazolyl)- N···Cl (2.9769 Å) distances as well as by the N–H–Cl angle
borato-ruthenium(II) complexes.[16] The small N–Ru–N (171°) close to 180°.[17] This interaction explains the low
angles, in the range 79.70–86.25°, reflect the fac environ- conductivity values obtained for 6b compared with the high
–
ment of the ligand around the ruthenium ion. The Ru–N values obtained for 6a, which has a BF4 counteranion.
Eur. J. Inorg. Chem. 2011, 4745–4755
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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4749

S. Miguel, J. Diez, M. P. Gamasa, M. E. Lastra
FULL PAPER
R-PTA)][Y] [R = CH3, Y = CF3SO3 (8); R = CH2Ph, Y =
Cl (9); R = CH2CH=CH2, Y = I (10)], which contain modi-
fied PTA ligands (Scheme 5). The complexes were isolated
in 64–74% yield. The molar conductivities in acetonitrile
(96–147 Scm2 mol–1) are in the range found for 1:1 electro-
lytes.
Figure 5. Hydrogen bonding in 6b.
Synthesis of [RuCl{κ3(N,N,N)-Tpms}(PPh3)(1-BH3-PTA)]
(7)
Scheme 5.
Complex 3 reacts with stoichiometric amounts of
BH3·THF in THF at room temperature to yield [RuCl-
{κ3(N,N,N)-Tpms}(PPh3)(1-BH3-PTA)][BF4] (7), which
precipitated upon addition of hexane (Scheme 4).
The spectroscopic data agree with the proposed stoichio-
metries. The more remarkable features are as follows: (i) the
IR spectra show characteristic absorptions for the
κ3(N,N,N) coordination mode of Tpms in 8–10, (ii) the
31P{1H} NMR spectra show two doublets in the range 39.1
to 39.8 ppm for PPh3 and –12.2 to –15.8 ppm for 1-R-PTA
(2JPP = 33 Hz). The chemical shift of the modified PTA
ligand, again clearly shifted to lower fields, agrees with the
1
N-alkylation of the PTA ligand, and (iii) the H NMR and
13C{1H} NMR spectra have been fully assigned through
COSY HH, HSQC, and HMBC NMR experiments and
agree with the proposed complexes (see Exp. Sect.).
Conclusions
Scheme 4.
New ruthenium(II) scorpionate complexes have been
synthesized and the coordination modes have been deter-
mined by X-ray diffraction. For complexes with Tpms, the
thermodynamic product 1a shows κ3(N,N,N) coordination
of the ligand. The kinetic product, 1b, which has κ3(N,N,O)-
Tpms coordination, was also isolated.
PPh3 substitution with PTA led to new complexes, which
exhibit very low water solubility. Surprisingly, the com-
plexes with Tpm show higher water solubility than those
with Tpms. Electrophilic attacks on coordinated PTA gave
rise to new PTA-substituted ruthenium(II) derivatives.
For 5b and 6b, hydrogen bonding interactions were estab-
lished between the NH proton and chlorine anions. This
interaction has been confirmed in 6b by X-ray analysis.
Complex 7 was isolated in 83% yield as a yellow air-
stable solid and the spectroscopic data agree with the pro-
posed stoichiometry. The more remarkable features are as
follows: (i) the IR spectrum shows the characteristic ab-
sorptions for Tpms coordinated in the κ3(N,N,N) mode
[1282, 1055 ν(S–O), 833 ν(C–N), and 622 ν(C–S) cm–1]. The
ν(B–H) absorptions are observed at 2370, 2292, and
2225 cm–1, and the ν(N–B) absorption at 1170 cm–1, (ii) the
31P{1H} NMR spectrum shows two doublets at 40.8 and
–27.8 ppm (2JPP = 34 Hz) for the PPh3 and the 1-BH3-PTA
ligands, respectively, (iii) the 11B{1H} NMR spectrum
shows the signal for the BH3 group at –10.40 ppm, and (iv)
1
the H and the 13C{1H} NMR spectra have been fully as-
signed through COSY HH, HSQC, and HMBC experi-
ments and agree with the proposed complexes.
Experimental Section
PTA Alkylation Reactions. Synthesis of [RuCl{κ3(N,N,N)-
Tpms}(PPh3)(1-R-PTA)][Y] [R = CH3, Y = CF3SO3 (8); R
= CH2Ph, Y = Cl (9); R = CH2CH=CH2, Y = I (10)]
General Procedures: All manipulations were performed under an
atmosphere of dry nitrogen using a vacuum line and standard
Schlenk techniques. All reagents were obtained from commercial
suppliers and used without further purification. Solvents were dried
by standard methods and distilled under nitrogen before use.
[RuCl2(PPh3)3],[18] LiTpms,[3] [RuCl{κ3(N,N,N)-Tpm}(PPh3)2]-
The reaction of 3 with methyl triflate or organic halides
such as benzyl chloride or allyl iodide in dichloromethane
at room temperature led to [RuCl{κ3(N,N,N)-Tp}(PPh3)(1- Cl,[16] Tpm,[19] and PTA[20] were prepared by reported methods. IR
4750
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 4745–4755

New Ruthenium(II) Complexes Containing Scorpionate Ligands
spectra were recorded with a Perkin–Elmer FT-IR Paragon 1000
spectrometer. Conductivities were measured at room temperature
in ca. 5ϫ10–4 moldm–3 solutions, with a crison EC-Meter BASIC
30+ conductimeter. The C, H, and N analyses were carried out
with a Perkin–Elmer 240-B microanalyzer. NMR spectra were re-
corded with Bruker AV400 and NAV400 instruments at 400.1 MHz
(1H), 100.6 MHz (13C), 162.1(31P), and 128.4 (11B) and Bruker
AV300 and 300DPX instruments at 300.1 MHz (1H) and
121.5 MHz (31P), using SiMe4 or 85% H3PO4 as standards. DEPT
experiments were carried out for all the compounds. Coupling con-
stants J are given in Hertz. Resonances due to the Tpm and Tpms
ligands are reported by chemical shift and multiplicity only, as all
3JH,H values for the pyrazolyl rings are 2 Hz. Abbreviations used:
br, broad signal; d, doublet; t, triplet; dd, double doublet; m, mul-
tiplet; sept, septuplet; s, singlet.
tration, washed with hexane, and dried under vacuum to give 3.
Yield: 66 mg (85%). C25H40ClN12O3P2RuS (787.1): calcd. C 38.14,
H 5.12, N 21.35, S 4.07; found C 37.75, H 4.93, N 20.14, S 3.88.
IR (KBr pellet): ν = 1278, 1053 [ν(S–O)], 813 [ν(C–N)], 622 [ν(C–
˜
1
S)] cm–1. H NMR (400.5 MHz, CDCl3, 20 °C): 9.24 [d, 1 H, 3-H
and 5-H (pz)], 9.05 [d, 2 H, 3-H and 5-H (pz)], 8.07 [d, 2 H, 3-H
and 5-H (pz)], 7.19 [d, 1 H, 3-H and 5-H (pz)], 6.45 [t, 2 H, 4-H
(pz)], 6.43 [t, 1 H, 4-H (pz)], 4.60 (AB spin system, 6 H, JHAHB
=
13 Hz, NCH2N), 4.48 (AB spin system, 6 H, JHAHB = 13 Hz,
NCH2N), 4.18 (s, 12 H, NCH2P) ppm. 13C{1H} NMR
(100.6 MHz, CDCl3, 20 °C): 148.2 [s, C-3 and C-5 (pz)], 145.3 [s,
C-3 and C-5 (pz)], 138.5 [s, C-3 and C-5 (pz)], 137.1 [s, C-3 and C-
5 (pz)], 107.5 [s, C-4 (pz)], 107.1 [s, C-4 (pz)], 90.8 (s, C-SO3), 73.3
3
(d, JCP = 6 Hz, NCH2N), 53.3 (d, JCP = 15 Hz, NCH2P) ppm.
31P{1H} NMR (162.1 MHz, CDCl3, 20 °C): –33.1 (s, PTA) ppm.
[RuCl{κ3(N,N,N)-Tpms}(PPh3)(PTA)] (3): To a solution of 1a
(145 mg, 0.15 mmol) in toluene (80 mL) was added PTA (28 mg,
0.15 mmol). The reaction mixture was heated to reflux for 4.5 h.
The solvent was evaporated under vacuum and the yellow solid
obtained was recrystallized from CH2Cl2/hexane. Yield: 100 mg
(79%). C34H36ClN9O3P2RuS (849.1): calcd. C 48.09, H 4.27, N
14.84, S 3.78; found C 48.72, H 4.50, N 14.98, S 3.57. IR (KBr
[RuCl{κ3(N,N,N)-Tpms}(PPh3)2] (1a): To
a
solution of
[RuCl2(PPh3)3] (120 mg, 0.13 mmol) in methanol (15 mL) was
added LiTpms (39 mg, 0.13 mmol). The reaction mixture was
heated to reflux for 4 h before the volatiles were removed in vacuo.
The solid residue was extracted into CH2Cl2, filtered through
kieselguhr, and concentrated under vacuum to a volume of approx.
1 mL. Addition of hexane afforded a yellow precipitate. The sol-
vents were decanted, and the solid residue was washed with hexane
(3ϫ30 mL) and dried under reduced pressure to afford 1a. Yield:
118 mg (95%). C47H41Cl3N6O3P2RuS (1038.1): calcd. C 54.32, H
3.98, N 8.09, S 3.09; found C 54.18, H 3.73, N 7.65, S 2.61. IR
pellet): ν = 1285, 1054 [ν(S–O)], 834 [ν(C–N)], 621 [ν(C–S)] cm–1.
˜
1H NMR (400.5 MHz, CDCl3, 20 °C): δ = 9.10 [d, 1 H, 3-H and
5-H (pz)], 9.04 [d, 1 H, 3-H and 5-H (pz)], 9.0 [d, 1 H, 3-H and 5-
H (pz)], 8.33 [d, 1 H, 3-H and 5-H (pz)], 7.61–7.34 (m, 15 H, PPh3),
6.77 [d, 1 H, 3-H and 5-H (pz)], 6.47 [t, 1 H, 4-H (pz)], 5.98 [t, 1
H, 4-H (pz)], 5.88 [m, 2 H, 3-H, 5-H, and 4-H (pz)], 4.45 (AB spin
system, JHAHB = 13 Hz, 3 H, NCH2N), 4.26 (AB spin system,
JHAHB = 13 Hz, 3 H, NCH2N), 3.91 (s, 6 H, NCH2P) ppm.
13C{1H} NMR (100.6 MHz, CDCl3, 20 °C): δ = 147.8 [s, C-3 and
C-5 (pz)], 145.8 [s, C-3 and C-5 (pz)], 145.3 [s, C-3 and C-5 (pz)],
137.7 [s, C-3 and C-5 (pz)], 137.1 [s, C-3 and C-5 (pz)], 136.9 [s, C-
(KBr pellet): ν = 1286 [ν(S–O)], 1054, 832 [ν(C–N)], 622 [ν(C–S)]
˜
1
cm–1. H NMR (400.5 MHz, CDCl3, 20 °C): δ = 9.10 [d, 1 H, 3-H
and 5-H (pz)], 8.91 [d, 2 H, 3-H and 5-H (pz)], 7.29–7.09 (m, 30
H, PPh3), 6.99 [d, 2 H, 3-H and 5-H (pz)], 5.85 [t, 2 H, 4-H (pz)],
5.42 [t, 1 H, 4-H (pz)], 5.21 [d, 1 H, 3-H and 5-H (pz)] ppm.
13C{1H} NMR (100.6 MHz, CDCl3, 20 °C): δ = 149.8 [s, C-3 and
C-5 (pz)], 147.1 [s, C-3 and C-5 (pz)], 137.5 [s, C-3 and C-5 (pz)],
136.9 [s, C-3 and C-5 (pz)], 134.3 (s, C-2, C-6 and C-3, C-5 PPh3),
132.7 (d, JC,P = 38 Hz, C-1 PPh3), 129.6 (s, C-4 PPh3), 128.0 (C-2,
C-6 and C-3, C-5 PPh3), 106.5 [s, C-4 (pz)], 105.7 [s, C-4 (pz)], 90.8
(s, CSO3) ppm. 31P{1H} NMR (121.5 MHz, CDCl3, 20 °C): δ =
38.9 (s, PPh3) ppm.
2
3 and C-5 (pz)] 133.8 (d, JCP = 9 Hz, C-2 and C-6 PPh3), 130.1
2
(s, C-4 PPh3), 128.5 (d, JCP = 9 Hz, C-3 and C-5 PPh3), 107.2 [s,
C-4 (pz)], 106.8 [s, C-4 (pz)], 106.6 [s, C-4 (pz)], 90.6 (s, CSO3), 73.2
3
(d, JCP = 6 Hz, NCH2N), 51.6 (d, JCP = 14 Hz, NCH2P) ppm.
2
31P{1H} NMR (161.9 MHz, CDCl3, 20 °C): δ = 43.5 (d, JPP
34 Hz, PPh3), –37.9 (d, JPP = 34 Hz, PTA) ppm.
=
2
[RuCl{κ3(N,N,O)-Tpms}(PPh3)2] (1b):
A solution of LiTpms
[RuCl{κ3(N,N,N)-Tpm}(PPh3)(PTA)][Cl] (4): To a solution of com-
plex [RuCl{κ3(N,N,N)-Tpm}(PPh3)2][Cl] (100 mg, 0.110 mmol) in
toluene (15 mL) was added PTA (17 mg, 0.110 mmol). The reaction
mixture was heated to reflux for 5 h. The solvent was evaporated
under vacuum, and the yellow solid obtained was recrystallized
(156 mg, 0.52 mmol) in methanol (5 mL) was added to a solution
of [RuCl2(PPh3)3] (500 mg, 0.52 mmol) in CH2Cl2 (50 mL) at 0 °C.
The mixture was stirred for 20 min and then evaporated to dryness.
The residue was extracted into CH2Cl2 and concentrated under
vacuum to a volume of approx. 1 mL. Addition of hexane afforded
an orange precipitate. The solvents were decanted, and the solid
residue was washed with hexane (3ϫ30 mL) and dried under re-
from CH2Cl2/hexane. Yield: 70 mg (79%). S20 °C (H2O)
=
2.8 mgmL–1. C34H37Cl2N9P2Ru (805.1): calcd. C 50.69, H 4.63, N
15.61; found C 50.67, H 4.94, N 15.61. Molar conductivity in nitro-
methane: ΛM = 76 Scm2 mol–1. 1H NMR (400.5 MHz, CD2Cl2,
20 °C): 12.24 (s, 1 H, Hapical), 8.87 [d, 1 H, 3-H and 5-H (pz)], 8.81
[d, 1 H, 3-H and 5-H (pz)], 8.74 [d, 1 H, 3-H and 5-H (pz)], 8.28
[d, 1 H, 3-H and 5-H (pz)], 7.71–7.37 (m, 15 H, PPh3), 6.74 [d, 1
H, 3-H and 5-H (pz)], 6.50 [d, 1 H, 4-H (pz)], 6.08 [d, 1 H, 4-H
(pz)], 5.97 [d, 1 H, 4-H (pz)], 5.86 [d, 1 H, 3-H and 5-H (pz)], 4.45
(AB spin system, 3 H, JHAHB = 14 Hz, NCH2N), 4.26 (AB spin
system, 3 H, JHAHB = 14 Hz, NCH2N), 3.96 (CD spin system, 3
duced pressure to afford 1b. Yield: 283 mg (57%). IR (KBr pellet):
1
ν = 1088, 860 [ν(C–N)], 621 [ν(C–S)] cm–1. H NMR (400.5 MHz,
˜
CDCl3, 20 °C): 9.00 [d, 1 H, 3-H and 5-H (pz)], 7.90 [d, 1 H, 3-H
and 5-H (pz)], 7.40–7.00 (m, 30 H, PPh3), 6.99 [d, 2 H, 3-H and 5-
H (pz)], 6.97 [d, 2 H, 3-H and 5-H (pz)], 6.60 [t, 1 H, 4-H (pz)],
5.79 [t, 2 H, 4-H (pz)] ppm. 13C{1H} NMR (100.6 MHz, CDCl3,
–20 °C): 148.6 [s, C-3 and C-5 (pz)], 142.9 [s, C-3 and C-5 (pz)],
136.6 [s, C-3 and C-5 (pz)], 135.4 [s, C-3 and C-5 (pz)], 135.1 (s, C-
2, C-6 and C-3, C-5 PPh3), 134.3 (s, C-1 PPh3), 129.1 (s, C-4 PPh3),
127.4 (s, C-2, C-6 and C-3, C-5 PPh3), 108.3 [s, C-4 (pz)], 106.4 [s,
C-4 (pz)], 94.7 (s, CSO3) ppm. 31P{1H} NMR (162.1 MHz, CDCl3,
20 °C): 35.8 (s, PPh3) ppm.
H, JHCHD = 15 Hz, NCH2P), 3.89 (CD spin system, 3 H, JHCHD
=
15 Hz, NCH2P) ppm. 13C{1H} NMR (100.6 MHz, CD2Cl2, 20 °C):
148.0 [s, C-3 and C-5 (pz)], 146.2 [s, C-3 and C-5 (pz)], 145.4 [s, C-
3 and C-5 (pz)], 134.6 [s, C-3 and C-5 (pz)], 134.3 [s, C-3 and C-5
[RuCl{κ3(N,N,N)-Tpms}(PTA)2] (2): To a solution of 1a (100 mg, (pz)], 133.7 (d, 2JCP = 9 Hz, C-2 and C-6 PPh3), 130.1 (s, C-4 PPh3),
0.105 mmol) in toluene (12 mL) was added PTA (38 mg,
0.241 mmol). The reaction mixture was heated to reflux for 6 h,
and a yellow precipitate formed. The solid was collected by fil-
128.5 (d, 2JCP = 9 Hz, C-3 and C-5 PPh3), 108.1 [s, C-4 (pz)], 107.9
3
[s, C-4 (pz)], 107.6 [s, C-4 (pz)], 73.2 (s, CH), 73.1 (d, JCP = 6 Hz,
NCH2N), 51.9 (d, JCP = 15 Hz, NCH2P) ppm. 31P{1H} NMR
Eur. J. Inorg. Chem. 2011, 4745–4755
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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4751

S. Miguel, J. Diez, M. P. Gamasa, M. E. Lastra
FULL PAPER
(161.9 MHz, CDCl3, 20 °C): 44.9 (d, 2JPP = 36 Hz, PPh3), –35.1 (d,
duced under vacuum to about 1 mL. The addition of hexane af-
forded a yellow precipitate. The solvent was decanted, and the solid
residue was washed with hexane and dried under vacuum. Yield:
94 mg (80%). C35H40B2Cl3F8N9P2Ru (1042.1): calcd. C 40.82, H
3.92, N 12.24; found C 40.3, H 4.76, N 13.63. Molar conductivity
in nitromethane: ΛM = 182 Scm2 mol–1. 1H NMR (300.13 MHz,
[D6]DMSO, 20 °C): δ = 9.91 (s, 1 H, Hapical), 8.48 [m, 3 H, 3-H
and 5-H (pz)], 8.42 [d, 1 H, 3-H and 5-H (pz)], 7.47–7.40 (m, 15
H, PPh3), 6.67 [d, 1 H, 3-H and 5-H (pz)], 6.64 [d, 1 H, 3-H and
5-H (pz)], 6.59 [d, 1 H, 4-H (pz)], 6.36 [d, 1 H, 4-H (pz)], 6.15 [d,
1 H, 4-H (pz)], 4.59 (AB spin system, JHAHB = 12 Hz, 3 H,
NCH2N), 4.47 (AB spin system, JHAHB = 12 Hz, 3 H, NCH2N),
3.87 (s, 6 H, NCH2P) ppm. 13C{1H} NMR (75.46 MHz, [D6]-
DMSO, 20 °C): δ = 150.9 [s, C-3 and C-5 (pz)], 147.8 [s, C-3 and
C-5 (pz)], 146.4 [s, C-3 and C-5 (pz)], 136.7 [s, C-3 and C-5 (pz)],
135.5 [s, C-3 and C-5 (pz)], 134.5 [s, C-3 and C-5 (pz)], 133.2 (s, C-
2 and C-6, PPh3), 130.9 (s, C-4, PPh3), 129.2 (s, C-3 and C-5, PPh3),
111.2 [s, C-4 (pz)], 109.3 [s, C-4 (pz)], 108.1 [s, C-4 (pz)], 75.3 (s,
CSO3), 71.3 (s, NCH2N, PTA), 49.1 (s, NCH2P, PTA) ppm.
2JPP = 36 Hz, PTA) ppm.
[RuCl{κ3(N,N,N)-Tpms}(PPh3)(1-H-PTA)][BF4] (5a): To a solution
of 3 (100 mg, 0.118 mmol) in CH2Cl2 (8 mL) at –30 °C was added
a diethyl ether solution of HBF4·OEt2 (36 μL, 0.142 mmol). The
reaction mixture was stirred at this temperature for 1.5 h. The yel-
low solution was filtered, and the filtrate was reduced under vac-
uum to about 1 mL. Addition of diethyl ether afforded a yellow
precipitate. The solvents were decanted, and the solid residue was
washed with diethyl ether and dried under vacuum. Yield: 88 mg
(79%). C36H41BCl3F4N9O3P2RuS (1105.1): calcd. C 39.06, H 3.73,
N 11.39, S 2.90; found C 38.28, H 4.49, N 11.46, S 3.19. Molar
conductivity in nitromethane: ΛM = 83 Scm2 mol–1. IR (KBr pel-
let): ν = 1296 [ν(S–O)], 835 [ν(C–N)], 622 [ν(C–S)], 1031 [ν(B–F)]
˜
cm–1. 1H NMR (300.13 MHz, CD3CN, 20 °C): δ = 9.01 [d, 1 H, 3-
H and 5-H (pz)], 8.98 [d, 2 H, 3-H and 5-H (pz)], 8.32 [d, 1 H, 3-
H and 5-H (pz)], 7.51–7.41 (m, 15 H, PPh3), 6.87 [d, 1 H, 3-H and
5-H (pz)], 6.58 [d, 1 H, 4-H (pz)], 6.46 [d, 1 H, 3-H and 5-H (pz)],
6.13 [d, 1 H, 4-H (pz)], 6.05 [d, 1 H, 4-H (pz)], 4.67 (AB spin
system, JHAHB = 12 Hz, 3 H, NCH2N), 4.49 (AB spin system,
2
31P{1H} NMR (162.1 MHz, [D6]DMSO, 20 °C): δ = 43.0 (d, JPP
= 34 Hz, PPh3), –24.2 (broad signal, PTA) ppm.
JHAHB = 12 Hz, 3 H, NCH2N), 3.91 (CD spin system, JHCHD
=
[RuCl{κ3(N,N,N)-Tpm}(PPh3)(1-H-PTA)][Cl]2 (6b): To a solution
of 4 (100 mg, 0.124 mmol) in CH2Cl2 (7 mL) at 0 °C was added a
2 n HCl·OEt2 solution (74 μL, 0.148 mmol). The reaction mixture
was stirred at this temperature for 1.5 h. The addition of hexane
(50 mL) afforded a yellow precipitate. The solvents were decanted,
and the solid residue was washed with hexane and dried under
vacuum. Yield: 74 mg (71%). C34H37Cl3N9P2Ru (841.1): calcd. C
48.55, H 4.43, N 12.65; found C 48.31, H 4.12, N 13.07. Molar
conductivity in nitromethane: ΛM = 67 Scm2 mol–1. 1H NMR
(300.1 MHz, CDCl3, 20 °C): 12.53 (s, 1 H, H apical), 8.98 [d, 1 H,
3-H and 5-H (pz)], 8.85 [d, 2 H, 3-H and 5-H (pz)], 8.26 [d, 1 H,
3-H and 5-H (pz)], 7.42–7.29 (m, 15 H, PPh3), 6.74 [d, 1 H, 3-H
and 5-H (pz)], 6.49 [d, 1 H, 4-H (pz)], 6.38 [d, 1 H, 3-H and 5-H
(pz)], 6.09 [d, 2 H, 4-H (pz)], 4.62 (AB spin system, JHAHB = 13 Hz,
3 H, NCH2N), 4.49 (AB spin system, JHAHB = 13 Hz, 3 H,
NCH2N), 4.05 (CD spin system, JHCHD = 15 Hz, 3 H, NCH2P),
3.85 (CD spin system, JHCHD = 15 Hz, 3 H, NCH2P) ppm.
13C{1H} NMR (100.6 MHz, CD3CN, 20 °C): 149.3 [s, C-3 and C-
5 (pz)], 145.7 [s, C-3 and C-5 (pz)], 137.3 [s, C-3 and C-5 (pz)],
13 Hz, 3 H, NCH2P), 3.45 (CD spin system, JHCHD = 13 Hz, 3 H,
NCH2P) ppm. 13C{1H} NMR (100.6 MHz, CD3CN, 20 °C): δ =
149.8 [s, C-3 and C-5 (pz)], 146.4 [s, C-3 and C-5 (pz)], 145.9 [s, C-
3 and C-5 (pz)], 137.4 [s, C-3 and C-5 (pz)], 137.0 [s, C-3 and C-5
2
(pz)], 136.9 [s, C-3 and C-5 (pz)], 133.7 (d, JCP = 9 Hz, C-2 and
C-6, PPh3), 133.2 (s, C-1 PPh3), 130.5 (s, C-4, PPh3), 128.8 (d, 2JCP
= 9 Hz, C-3 and C-5, PPh3), 107.8 [s, C-4 (pz)], 107.6 [s, C-4 (pz)],
3
106.9 [s, C-4 (pz)], 90.6 (s, CSO3), 71.5 (d, JCP = 6 Hz, NCH2N,
PTA), 48.1 (d, JCP = 14 Hz, NCH2P, PTA) ppm. 31P{1H} NMR
2
(121.5 MHz, CD3CN, 20 °C): δ = 39.9 (d, JPP = 34 Hz, PPh3),
2
–19.6 (d, JPP = 34 Hz, PTA) ppm.
[RuCl{κ3(N,N,N)-Tpms}(PPh3)(1-H-PTA)][Cl] (5b): To a solution
of 3 (100 mg, 0.118 mmol) in CH2Cl2 (6 mL) at 0 °C was added a
2 n HCl·OEt2 solution (71 μL, 0.142 mmol). The reaction mixture
was stirred at this temperature for 2.5 h. The addition of hexane
(50 mL) afforded a yellow precipitate. The solvents were decanted,
and the solid residue was washed with hexane (2ϫ30 mL) and
dried under vacuum. Yield: 89 mg (86%). C40H51Cl2N9O3P2RuS
(971.1): calcd. C 49.43, H 5.29, N 12.97, S 3.30; found C 49.30, H
2
136.8 [s, C-3 and C-5 (pz)], 133.1 (d, C-2 and C-6, JCP = 9 Hz,
5.39, N 13.09, S 3.59. Molar conductivity in nitromethane: ΛM
=
PPh3), 132.8 (s, C-1 PPh3), 130.5 (s, C-4, PPh3), 128.5 (d, C-3 and
C-5, 2JCP = 9 Hz, PPh3), 107.3 [s, C-4 (pz)], 105.9 [s, C-4 (pz)], 90.4
(s, CSO3), 71.4 (S, NCH2N, PTA), 48.9 (s, NCH2P, PTA) ppm.
65 Scm2 mol–1. IR (KBr pellet): ν = 1282, 1055 [ν(S–O)], 835 [ν(C–
˜
N)], 622 [ν(C–S)] cm–1. 1H NMR (400.1 MHz, CD2Cl2, 20 °C):
9.09 [d, 1 H, 3-H and 5-H (pz)], 9.01 [d, 2 H, 3-H and 5-H (pz)],
8.31 [d, 1 H, 3-H and 5-H (pz)], 7.55–7.40 (m, 15 H, PPh3), 6.85
[d, 1 H, 3-H and 5-H (pz)], 6.52 [d, 1 H, 4-H (pz)], 6.23 [d, 1 H, 3-
H and 5-H (pz)], 6.07 [d, 1 H, 4-H (pz)], 6.02 [d, 1 H, 4-H (pz)],
4.64–4.44 (broad signal, 6 H, NCH2N), 4.02–3.89 (broad signal, 6
H, NCH2P) ppm. 13C{1H} NMR (100.6 MHz, CD3CN, 20 °C):
148.6 [s, C-3 and C-5 (pz)], 146.0 [s, C-3 and C-5 (pz)], 137.6 [s, C-
3 and C-5 (pz)], 137.1 [s, C-3 and C-5 (pz)], 133.6 (d, C-2 and C-
2
31P{1H} NMR (121.4 MHz, CDCl3, 20 °C): 40.7 (d, JPP = 34 Hz,
2
PPh3), –20.7 (d, JPP = 34 Hz, PTA) ppm.
[RuCl{κ3(N,N,N)-Tpms}(PPh3)(1-BH3-PTA)] (7): To a solution of
3 (50 mg, 0.059 mmol) in tetrahydrofuran (5 mL) was added
BH3·THF (60 μL, 0.059 mmol), and the mixture was stirred for 1 h
at room temperature. The addition of hexane (50 mL) afforded a
yellow precipitate. The solvents were decanted, and the solid resi-
due was washed with hexane and dried under vacuum. Yield: 42 mg
(83%). C34H39BClN9O3P2RuS (863.1): calcd. C 47.31, H 4.55, N
14.61, S 3.72; found C 46.88, H 4.39, N 14.40, S 3.60. IR (KBr
2
6, JCP = 9 Hz, PPh3), 133.1 (s, C-1, PPh3), 130.5 (s, C-4, PPh3),
128.7 (d, C-3 and C-5, 2JCP = 9 Hz, PPh3), 107.5 [s, C-4 (pz)], 106.6
[s, C-4 (pz)], 90.6 (s, CSO3), 71.6 (s, NCH2N), 49.3 (broad s,
NCH2P) ppm. 31P{1H} NMR (121.5 MHz, CD2Cl2, 20 °C): 39.6
pellet): ν = 1282, 1055 [ν(S–O)], 833 [ν(C–N)], 622 [ν(C–S)], 2370,
˜
2292, 2225 [ν(B–H)], 1170 [ν(N–B)] cm–1. 1H NMR (400.1 MHz,
CD2Cl2, 20 °C): δ = 9.1 [d, 1 H, 3-H and 5-H (pz)], 9.01 [d, 2 H,
3-H and 5-H (pz)], 8.26 [d, 1 H, 3-H and 5-H (pz)], 7.55–7.39 (m,
15 H, PPh3), 6.86 [d, 1 H, 3-H and 5-H (pz)], 6.52 [d, 1 H, 4-H
(pz)], 6.18 [d, 1 H, 3-H and 5-H (pz)], 6.06 [d, 1 H, 4-H (pz)], 6.01
2
2
(d, JPP = 33 Hz, PPh3), –23.4 (d, JPP = 33 Hz, PTA) ppm.
[RuCl{κ3(N,N,N)-Tpm}(PPh3)(1-H-PTA)][BF4]2 (6a): Complex 4
(100 mg, 0.124 mmol) was dissolved in CH2Cl2 (10 mL), and the
yellow solution was cooled to –30 °C and stirred for 15 min. NaBF4
(136 mg, 1.24 mmol) and HBF4·OEt2 (22 μL, 0.149 mmol) were [d, 1 H, 4-H (pz)], 4.20 (m, 6 H, NCH2N), 3.70 (m, 6 H, NCH2P),
added. The mixture was stirred at this temperature for 1.5 h. The
solution was filtered through kieselghur, and the filtrate was re-
1.19 (broad, 3 H, PTA–BH3) ppm. 11B{1H} NMR (128.4 MHz,
CD2Cl2, 20 °C): δ = –10.40 ppm. 13C{1H} NMR (100.6 MHz,
4752
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 4745–4755

New Ruthenium(II) Complexes Containing Scorpionate Ligands
CD2Cl2, 20 °C): δ = 148.4 [s, C-3 and C-5 (pz)], 145.9 [s, C-3 and
C-5 (pz)], 145.7 [s, C-3 and C-5 (pz)], 137.8 [s, C-3 and C-5 (pz)],
137.1 [s, C-3 and C-5 (pz)], 137.0 [s, C-3 and C-5 (pz)], 133.7 (d,
137.1 [s, C-3 and C-5 (pz)], 137.0 [s, C-3 and C-5 (pz)], 133.9 (d,
C-2 and C-6 PPh3), 133.4 (s, C-1 PPh3), 131.0 (s, C-4 PPh3), 129.2
(d, C-3 and C-5 PPh3), 128.9 (s, NCH2CH=CH2), 124.1 (s,
NCH2CH=CH2), 108.5 [s, C-4 (pz)], 107.8 [s, C-4 (pz)], 107.7 [s,
2
C-2 and C-6, JCP = 9 Hz, PPh3), 133.3 (s, C-1 PPh3), 130.4 (s, C-
2
4 PPh3), 128.6 (d, C-3 and C-5, JCP = 9 Hz, PPh3), 107.2 [s, C-4 C-4 (pz)], 90.6 (s, CSO3), 79.2 (s, NCH2NCH2CH=CH2), 77.9 (s,
(pz)], 107.1 [s, C-4 (pz)], 106.6, [s, C-4 (pz)], 90.6 (s, CSO3), 77.6,
(s, NCH2N, PTA), 70.8, (d, NCH2N, PTA), 67.7 (s, NCH2N, PTA), NCH2CH=CH2), 50.8, (d, JCP = 9 Hz, NCH2P), 46.9 (d, JCP
NCH2NCH2CH=CH2),
72.3
(s,
NCH2N),
68.7
(s,
=
54.7 (d, JCP = 15 Hz, NCH2P, PTA), 48.9 (d, JCP = 15 Hz, NCH2P, 9 Hz, PCH2NCH2CH=CH2), 46.6 (d, JCP = 9 Hz, NCH2P) ppm.
2
PTA), 48.7 (d, JCP = 15 Hz, NCH2P, PTA) ppm. 31P{1H} NMR 31P{1H} NMR (162.1 MHz, [D6]DMSO, 20 °C): δ = 39.8 (d, JPP
2
2
(162.1 MHz, CD2Cl2, 20 °C): δ = 40.8 (d, JPP = 34 Hz, PPh3),
–27.8 (d, JPP = 34 Hz, PTA) ppm.
= 33 Hz, PPh3), –15.2 (d, JPP = 33 Hz, PTA) ppm.
2
[RuCl{κ3(N,N,N)-Tpms}(PPh3)(1-PhCH2-PTA)][Cl] (10): Benzyl
chloride (70 μL) was added to a solution 2 (100 mg, 0.12 mmol)
in CH2Cl2 (5 mL). The reaction mixture was stirred for 24 h. The
addition of hexane (50 mL) afforded 8. The solvents were decanted,
and the solid residue was washed with hexane and dried under
reduced pressure. Yield: 90 mg (77%). C42H45Cl4N9O3P2RuS
(1059.1): calcd. C 47.56, H 4.28, N 11.88, S 3.02; found C 48.19,
[RuCl{κ3(N,N,N)-Tpms}(PPh3)(1-CH3-PTA)][CF3SO3] (8): Com-
plex 3 (100 mg, 0.118 mmol) was dissolved in CH2Cl2 (2 mL) at
–30 °C. After 15 min, methyl trifluoromethanesulfonate (14 μL,
0.118 mmol) was added and the reaction mixture was stirred for 1 h
at low temperature. Addition of hexane (50 mL) afforded a yellow
precipitate. The solvents were decanted, and the solid residue was
washed with hexane and dried under vacuum. Yield: 77 mg (65%).
C36H39ClF3N9O6P2RuS2 (1013.1): calcd. C 42.67, H 3.88, N 12.44,
S 6.33; found C 41.91, H 4.00, N 12.01, S 5.81. Molar conductivity
H 4.96, N 11.65, S 3.26. Molar conductivity in acetonitrile: ΛM
=
119 Scm2 mol–1. IR (KBr pellet): ν = 1293, 1054 [ν(S–O)], 834
˜
[ν(C–N)], 621 [ν(C–S)] cm–1. 1H NMR (300.1 MHz, CD3CN,
20 °C): 8.98 [d, 2 H, 3-H and 5-H (pz)], 8.94 [d, 1 H, 3-H and 5-H
(pz)], 8.52 [d, 1 H, 3-H and 5-H (pz)], 7.50–7.32 (m, 20 H, PPh3
and Ph), 6.85 [d, 1 H, 3-H and 5-H (pz)], 6.61 [d, 1 H, 3-H and 5-
H (pz)], 6.56 [d, 1 H, 4-H (pz)], 6.12 [d, 1 H, 4-H (pz)], 6.02 [d, 1
H, 4-H (pz)], 5.36–5.32 (m, 2 H, PhCH2NCH2N), 4.83–4.75 (m, 2
H, PhCH2NCH2N), 4.54–4.41 (m, 4 H, PhCH2 and NCH2N),
4.16–4.11 (m, 2 H, PhCH2NCH2P), 3.75–3.70 (m, 4 H, NCH2P)
ppm. 13C{1H} NMR (100.6 MHz, CD3CN, 20 °C): 150.7 [s, C-3
and C-5 (pz)], 147.2 [s, C-3 and C-5 (pz)], 145.9 [s, C-3 and C-5
(pz)], 137.3 [s, C-3 and C-5 (pz)], 136.9 [s, C-3 and C-5 (pz)], 136.8
[s, C-3 and C-5 (pz)], 133.7–125.6 (Ph and PPh3), 107.9 [s, C-4
(pz)], 107.6 [s, C-4 (pz)], 106.9 [s, C-4 (pz)], 90.6 (s, CSO3), 79.3 (s,
PhCH2NCH2N), 78.2 (s, PhCH2NCH2N), 68.9 (s, NCH2N), 64.1
in acetonitrile: ΛM = 147 Scm2 mol–1. IR (KBr pellet): ν = 1278,
˜
1030 [ν(S–O)], 835 [ν(C–N)], 623 [ν(C–S)] cm–1. 1H NMR
(300.1 MHz, CD3CN, 20 °C): 9.05 [d, 1 H, 3-H and 5-H (pz)], 9.01
[d, 1 H, 3-H and 5-H (pz)], 8.99 [d, 1 H, 3-H and 5-H (pz)], 8.33
[d, 1 H, 3-H and 5-H (pz)], 7.55–7.40 (m, 15 H, PPh3), 6.88 [d, 1
H, 3-H and 5-H (pz)], 6.73 [d, 1 H, 3-H and 5-H (pz)], 6.57 [t, 1
H, 4-H (pz)], 6.16 [t, 1 H, 4-H (pz)], 6.11 [t, 1 H, 4-H (pz)], 4.74–
4.56 (m, 2 H, CH3NCH2N), 4.29–4.24 (m, 4 H, NCH2N), 4.17–
3.92 (m, 2 H, CH3NCH2P), 3.86–3.30 (m, 4 H, NCH2P), 2.62 (s, 3
H, NCH3) ppm. 13C{1H} NMR (100.6 MHz, CD3CN, 20 °C):
150.3 [s, C-3 and C-5 (pz)], 146.7 [s, C-3 and C-5 (pz)], 145.9 [s, C-
3 and C-5 (pz)], 137.5 [s, C-3 and C-5 (pz)], 137.1 [s, C-3 and C-5
(pz)], 137.0 [s, C-3 and C-5 (pz)], 133.8 (d, C-2 and C-6, JCP
9 Hz, PPh3), 133.2 (s, C-1, PPh3), 130.6 (s, C-4, PPh3) 128.7 (d, C-
3 and C-5, JCP = 9 Hz, PPh3), 117.3 (q, JCF = 314 Hz, CF3SO3),
107.8 [s, C-4 (pz)], 107.5 [s, C-4 (pz)], 107.0 [s, C-4 (pz)], 90.7 (s,
CSO3), 80.5 (s, CH3NCH2N), 68.8 (d, JCP = 5 Hz, NCH2N), 56.3
2
=
(s, PhCH2N), 51.9 (d, JCP = 15 Hz, PhCH2NCH2P), 47.0 (d, JCP
=
3
15 Hz, NCH2P) ppm. 31P{1H} NMR (121.5 MHz, CD3CN, 20 °C):
2
2
39.9 (d, JPP = 33 Hz, PPh3), –12.2 (d, JPP = 33 Hz, PTA) ppm.
3
X-Ray Crystal Structure Determination of Complexes 1a, 1b, 2, 3,
5a, and 6b: Relevant crystal and refinement data are collected in
Table 4 and Table 5.
(d, JCP = 9 Hz, CH3NCH2P), 49.3 (s, NCH3), 47.2 (d, JCP = 15 Hz,
NCH2P) ppm. 31P{1H} NMR (121.5 MHz, CD3CN, 20 °C): 39.1
2
2
(d, JPP = 33 Hz, PPh3), –15.8 (d, JPP = 33 Hz, PTA) ppm.
[RuCl{κ3(N,N,N)-Tpms}(PPh3)(1-CH2=CHCH2-PTA)][I] (9): Allyl
iodide (22 μL, 0.24 mmol) was added to a solution of 3 (100 mg,
0.12 mmol) in CH2Cl2 (8 mL). The reaction mixture was stirred at
room temperature for 2 h. The addition of hexane (50 mL) afforded
9 as a yellow solid. The solvents were decanted, and the solid resi-
due was washed with hexane and dried under reduced pressure.
Yield: 101 mg (83%). C38H43Cl3IN9O3P2RuS (1101.0): calcd. C
41.41, H 3.93, N 11.44, S 2.91; found C 41.48, H 4.62, N 11.20, S
3.13. Molar conductivity in acetonitrile: ΛM = 96 Scm2 mol–1. IR
Data collection was performed at 293(2) K with an Oxford Diffrac-
tion Xcalibur Nova single crystal diffractometer using Cu-Kα radia-
tion (λ = 1.5418 Å) (1a, 1b, 2, 5a, and 6b). Images were collected
at a 65 mm fixed crystal-detector distance using the oscillation
method, with 1° oscillation and variable exposure time per image
3–20, 20–100, 3–5, 20–70, and 20–130 s for 1a, 1b, 2, 5a, and 6b,
respectively. Diffraction data for 3 were recorded with an Oxford
Diffraction Gemini S single crystal diffractometer using Cu-Kα ra-
diation (λ = 1.5418 Å) Images were collected at a 55 mm fixed crys-
tal-detector distance using the oscillation method, with 1° oscilla-
(KBr pellet): ν = 1281, 1054 [ν(S–O)], 856 [ν(C–N)], 621 [ν(C–S)],
˜
1
1623 [ν(C=C)] cm–1. H NMR (400.1 MHz, [D6]DMSO, 20 °C): δ tion and variable exposure time per image 5–50 s. In all cases the
= 8.95 [d, 1 H, 3-H and 5-H (pz)], 8.92 [d, 1 H, 3-H and 5-H (pz)],
8.88 [d, 1 H, 3-H and 5-H (pz)], 8.43 [d, 1 H, 3-H and 5-H (pz)],
7.53–7.41 (m, 15 H, PPh3), 7.10 [d, 1 H, 3-H and 5-H (pz)], 6.70
[d, 1 H, 4-H (pz)], 6.68 [d, 1 H, 3-H and 5-H (pz)], 6.34 [d, 1 H, 4-
data collection strategy was calculated with the program CrysAlis
Pro CCD.[21] Data reduction and cell refinement was performed
with the program CrysAlis Pro RED.[21] An empirical absorption
correction was applied using the SCALE3 ABSPACK algorithm as
implemented in the program CrysAlis Pro RED.[21] The software
H
(pz)], 6.24 [d, 1 H, 4-H (pz)], 5.82–5.76 (m, 1 H,
NCH2CH=CH2), 5.63–5.59 (m, 2 H, NCH2CH=CH2), 4.94–4.88 package WINGX[22] was used for space group determination,
(m, H, NCH2NCH2CH=CH2), 4.77–4.69 (m, H, structure solution, and refinement. The structures of the complexes
2
2
NCH2NCH2CH=CH2), 4.33–4.15 (m, 4 H, NCH2N), 4.09–4.05 were solved by Patterson interpretation and phase expansion using
(m, 2 H, PCH2NCH2CH=CH2), 3.85–3.77 (m, 4 H, NCH2P), 3.65 DIRDIF.[23] Isotropic least-squares refinement on F2 using
(d, 2 H, NCH2CH=CH2) ppm. 13C{1H} NMR (100.7 MHz, [D6]- SHELXL97[24] was performed. During the final stages of refine-
DMSO, 20 °C): δ = 151.5 [s, C-3 and C-5 (pz)], 147.7 [s, C-3 and
C-5 (pz)], 145.8 [s, C-3 and C-5 (pz)], 137.6 [s, C-3 and C-5 (pz)],
ment, all the positional parameters and the anisotropic temperature
factors of all the non-H atoms were refined, except C atoms of the
Eur. J. Inorg. Chem. 2011, 4745–4755
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4753

S. Miguel, J. Diez, M. P. Gamasa, M. E. Lastra
FULL PAPER
Table 4. Crystal data and structure refinement for 1a, 1b, and 2.
1a·CH2Cl2
1b·THF
2·4H2O
Chemical formula
fw
C47H41Cl3N6O3P2RuS
1039.28
C50H47ClN6O4P2RuS
1026.46
C22H41ClN12O7P2RuS
816.19
Crystal system
Space group
a [Å]
b [Å]
c [Å]
triclinic
P1
12.3238(3)
13.1656(3)
16.0094(4)
93.653(2)
monoclinic
P21/c
17.7447(1)
14.3433(1)
18.0578(2)
90
triclinic
P1
11.0589(2)
12.2137(2)
13.4458(3)
97.540(2)
¯
¯
α [°]
β [°]
95.020(2)
92.992(1)
90
4589.76(7)
4
1.485
4.815
97.944(2)
γ [°]
116.650(2)
2297.15(10)
2
1.503
5.847
115.980(2)
1578.98(5)
2
1.717
6.926
V [Å3]
Z
ρcalcd. [gcm–3]
μ [mm–1]
F(000)
1060
2112
840
Crystal size [mm]
θ range [°]
Index ranges
0.21ϫ0.17ϫ0.11
3.78 to 64.34
–14 Յ h Յ 14
–15 Յ k Յ 15
–18 Յ l Յ 18
32232
7693 [R(int) = 0.0336]
99.9
568/0
0.074ϫ0.054ϫ0.025
3.94 to 66.84
–21 Յ h Յ 21
–13 Յ k Յ 17
–16 Յ l Յ 21
24408
8053 [R(int) = 0.0548]
98.8
561/7
0.1ϫ0.09ϫ0.07
3.40 to 73.88
–13 Յ h Յ 12
–15 Յ k Յ 15
–16 Յ l Յ 16
32686
6310 [R(int) = 0.0223]
98.6
447/8
Reflections collected
Unique reflections
Completeness to θ max. [%]
Parameters/restraints
Goodness-of-fit on F2
1.059
0.819
1.066
[a]
[a]
R1 [I Ͼ 2σ(I)]; wR2 [I Ͼ 2σ(I)]
R1(all data); wR2(all data)
0.0381; 0.1074
0.0689; 0.0907
1.168 and –1.299
0.0392; 0.0861
0.0410; 0.1092
1.151 and –0.625
0.0207; 0.0529
0.0219; 0.0558
0.302 and –0.526
Largest diff. peak and hole [eÅ–3]
2
2 2
[a] R1 = Σ(|Fo| – |Fc|)/Σ|Fo|; wR2 = {Σ[w(Fo – Fc ) ]/Σ[w(Fo2)2]}1/2
.
Table 5. Crystal data and structure refinement for 3, 5a, and 6b.
3·2C3H6O
5a·2 NCMe
6b
Chemical formula
fw
C37H42ClN9O4P2RuS
907.32
C38H43BClF4N11O3P2RuS
1019.16
C35H40Cl5N9P2Ru
927.02
Crystal system
Space group
a [Å]
b [Å]
c [Å]
monoclinic
P21/c
17.8466(3)
10.0996(2)
22.7777(4)
90
monoclinic
P21/c
19.0825(3)
10.1250(2)
21.9137(3)
90
orthorhombic
Pbca
19.1872(4)
16.2722(3)
25.2421(8)
90
α [°]
β [°]
104.394(2)
90
3976.66(12)
4
1.515
5.492
97.5300(10)
90
4197.44(12)
4
1.613
5.409
90
90
7881.0(3)
8
1.563
γ [°]
V [Å3]
Z
ρcalcd. [gcm–3]
μ [mm–1]
F(000)
7.429
3776
1864
2080
Crystal size [mm]
θ range [°]
Index ranges
0.102ϫ0.061ϫ0.02
4.01 to 70.66
–21 Յ h Յ 21
–10 Յ k Յ 12
–27 Յ l Յ 16
14982
7423 [R(int) = 0.0479]
97.3
498/0
0.091ϫ0.075ϫ0.034
4.07 to 74.30
–22 Յ h Յ 23
–12 Յ k Յ 8
–27 Յ l Յ 25
16214
8205 [R(int) = 0.0257]
95.9
731/0
0.155ϫ0.052ϫ0.022
3.97 to 61.49
–21 Յ h Յ 15
–18 Յ k Յ 15
–28 Յ l Յ 28
23311
6004 [R(int) = 0.0891]
98.0
477/1
Reflections collected
Unique reflections
Completeness to θ max. [%]
Parameters/restraints
Goodness-of-fit on F2
0.840
1.127
0.834
[a]
[a]
R1 [I Ͼ 2σ(I)]; wR2 [I Ͼ 2σ(I)]
R1(all data); wR2(all data)
0.0357; 0.0743
0.0649; 0.0809
0.402 and –0.717
0.0336; 0.0944
0.0376; 0.1051
0.714 and –1.349
0.0585; 0.1392
0.1242; 0.1550
0.919 and –0.761
Largest diff. peak and hole [eÅ–3]
[a] R1 = Σ(|Fo| – |Fc|)/Σ|Fo|; wR2 = {Σ[w(Fo – Fc ) ]/Σ[w(Fo2)2]}1/2
.
2
2 2
C4H8 solvent molecule for 1b (these disordered atoms were located
geometrically located and their coordinates were refined riding on
by difference maps and isotropically refined). The H atoms were
their parent atoms, except hydrogen atoms of water molecules in 2,
4754
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 4745–4755

New Ruthenium(II) Complexes Containing Scorpionate Ligands
C. Dinoi, M. F. C. Guedes da Silva, A. J. L. Pombeiro, J. Or-
ganomet. Chem. 2008, 693, 2338–2344.
[8] C. M. Nagaraja, M. Nethaji, B. R. Jagirdar, Organometallics
2007, 26, 6307–6311.
[9] a) A. García-Fernandez, J. Díez, A. Manteca, J. Sánchez, M. P.
Gamasa, E. Lastra, Polyhedron 2008, 27, 1214–1228; b) A.
García-Fernandez, J. Díez, A. Manteca, J. Sanchez, R. García-
Nava, B. G. Sierra, F. Mollinedo, M. P. Gamasa, E. Lastra,
Dalton Trans. 2010, 39, 10186–10196.
[10] T. B. Chenskaya, M. Berghahn, P. C. Kunz, W. Frank, W.
Kläui, J. Mol. Struct. 2007, 829, 135–148.
hydrogen atoms in 5a, and H7n and H1 in 6b (the coordinates of
these H atoms were found from different Fourier maps and in-
cluded in a refinement with isotropic parameters). The minimized
2
2
function was [(ΣwFo – Fc )/Σw(Fo2)]1/2 where w = 1/[σ2(Fo2) +
(aP)2 + bP] (a and b values are collected in Table 3) with σ(Fo2)
2
from counting statistics and P = [Max (Fo2, 0) + 2Fc ]/3. Atomic
scattering factors were taken from the International Tables for X-
ray Crystallography.[25] Geometrical calculations were made with
PARST.[26] The crystallographic plots were made with PLATON[27]
and ORTEP-3 for Windows.[28]
[11] a) R. Wanke, P. Smolenski, M. F. C. Guedes da Silva,
L. M. D. R. S. Martins, A. J. L. Pombeiro, Inorg. Chem. 2008,
47, 10158–10168; b) W. Kläui, M. Berghahn, W. Frank, G. J.
Reiß, T. Schönherr, G. Rheinwald, H. Lang, Eur. J. Inorg.
Chem. 2003, 2059–2070.
[12] a) S. Pavlik, K. Mereiter, M. Puchberger, K. Kirchner, J. Or-
ganomet. Chem. 2005, 690, 5497–5507, and references cited
therein; b) M. Jiménez-Tenorio, M. D. Palacios, M. C. Puerta,
P. Valerga, Organometallics 2005, 24, 3088–3098, and refer-
ences cited therein; c) T. G. Appleton, H. C. Clark, L. E.
Manzer, Coord. Chem. Rev. 1973, 10, 335–422.
[13] L. D. Field, B. A. Messerle, L. Soler, I. E. Buys, T. W. Hambley,
J. Chem. Soc., Dalton Trans. 2001, 1959–1965.
[14] W. J. Geary, Coord. Chem. Rev. 1971, 7, 81–122.
[15] A. García-Fernandez, J. Díez, M. P. Gamasa, E. Lastra, Inorg.
Chem. 2009, 48, 2471–2481.
CCDC-830526 (for 1a), -830527 (for 1b), -830528 (for 2), -830529
(for 3), -830530 (for 5a), and -830531 (for 6b) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgments
This work was supported by the Spanish Ministerio de Ciencia e
Innovación (MICINN) (BQU2006-08485 and BQU2010-17005)
and Consolider Ingenio 2010 (CSD2007-00006).
[1] a) C. Pettinari, C Santini, in: Comprehensive Coordination
Chemistry II (Eds.: J. A. McCleverty, T. J. Meyer), Elsevier,
2003, vol. 1, pp. 159–210; b) S. Trofimenko, Scorpionates, The
Coordination Chemistry of Polypyrazolylborate Ligands, Impe-
rial College Press, 1999; c) C. Slugovc, I. Padilla-Martinez, S.
Sirol, E. Carmona, Coord. Chem. Rev. 2001, 213, 129–157; d)
M. D. Ward, J. A. McCleverty, J. C. Jeffery, Coord. Chem. Rev.
2001, 222, 251–272; e) D. L. Reger, Coord. Chem. Rev. 1996,
147, 571–595.
[16] B. Buriez, I. D. Burns, A. F. Hill, A. J. P. White, D. J. Williams,
J. D. E. T. Wilton-Ely, Organometallics 1999, 18, 1504–1516.
[17] a) T. Steiner, Angew. Chem. 2002, 114, 50; Angew. Chem. Int.
Ed. 2002, 41, 48–76; b) T. Steiner, Cryst. Rev. 1996, 1–57; c)
G. A. Jeffrey, H. Maluszynska, J. Mitra, Int. J. Biol. Macromol.
1985, 7, 336–348.
[18] T. A. Stephenson, G. Wilkinson, J. Inorg. Nucl. Chem. 1966,
28, 945–956.
[2] C. Pettinari, R. Pettinari, Coord. Chem. Rev. 2005, 249, 525–
[19] D. L. Reger, T. C. Grattan, K. J. Brown, C. A. Little, J. J. S.
Lamba, A. L. Rheingold, R. D. Sommer, J. Organomet. Chem.
2000, 607, 120–131.
543.
[3] W. Kläui, M. Berghahn, G. Rheinwald, H. Lang, Angew.
Chem. 2000, 112, 2590; Angew. Chem. Int. Ed. 2000, 39, 2464–
2466.
[20] D. J. Daigle, Inorg. Synth. 1998, 32, 40–45.
[21] CrysAlisPro CCD, CrysAlisPro RED, Oxford Diffraction Ltd.,
Abingdon, Oxfordshire, UK, 2008.
[4] a) D. V. Fomitchev, C. C. McLauchlan, R. H. Holm, Inorg.
Chem. 2002, 41, 958–966; b) R. S. Herrick, T. J. Brunker, C.
Maus, K. Crandall, A. Cetin, C. J. Ziegler, Chem. Commun.
2006, 4330–4331; c) E. C. B. Alegria, L. M. D. R. S. Martins,
M. Haukka, A. J. L. Pombeiro, Dalton Trans. 2006, 4954–4961.
[5] a) C. Dinoi, M. F. Guedes da Silva, C. B. A. Elisabete, P. Smo-
lenski, L. M. D. R. S. Martins, R. Poli, A. J. L. Pombeiro, Eur.
J. Inorg. Chem. 2010, 2415–2424; b) C. C. McLauchlan, M. P.
Weberski, B. A. Greiner, Inorg. Chim. Acta 2009, 362, 2662–
2666; c) C. Santini, M. Pellei, G. Lobbia, G. Gioia, A. Cingol-
ani, R. Spagna, M. Camalli, Inorg. Chem. Commun. 2002, 5,
430–433.
[22] L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837.
[23] P. T. Beurskens, G. Beurskens, R. de Gelder, J. M. M. Smits, S.
García-Granda, R. O. Gould, C. Smykalla, The DIRDIF Pro-
gram System, Technical Report of the Crystallographic Labo-
ratory, University of Nijmegen, The Netherlands, 2008.
[24] G. M. Sheldrick, SHELXL97: Program for the Refinement of
Crystal Structures; University of Göttingen, Germany, 2008.
[25] International Tables for X-ray Crystallography, Kynoch Press,
Birminghan, U. K., 1974, vol. IV (present distributor: Kluwer
Academic Publishers, Dordrecht, The Netherlands).
[26] M. Nardelli, Comput. Chem. 1983, 7, 95–98.
[6] E. T. Papish, M. T. Taylor, F. E. Jernigan III, M. J. Rodig,
R. R. Shawhan, G. P. A. Yap, F. A. Jove, Inorg. Chem. 2006,
45, 2242–2250.
[7] a) W. Kläui, D. Schramm, W. Peters, Eur. J. Inorg. Chem. 2001,
3113–3117; b) W. Kläui, D. Schramm, W. Peters, G. Rheinwald,
H. Lang, Eur. J. Inorg. Chem. 2001, 1415–1424; c) P. Smolenski,
[27] A. L. Spek, PLATON: A Multipurpose Crystallographic Tool,
University of Utrecht, The Netherlands, 2005.
[28] ORTEP-3 for Windows®: L. J. Farrugia, J. Appl. Crystallogr.
1997, 30, 565.
Received: June 20, 2011
Published Online: September 9, 2011
Eur. J. Inorg. Chem. 2011, 4745–4755
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4755