Synthesis, some properties, and crystalline modifications of fac-[Ru(NO)(Py)2Cl3]

Article abstract of DOI:10.1134/S1070328416120046

According to the data of ¹H NMR spectroscopy, trans-hydroxochloro complexes containing from two to four pyridine molecules in the internal sphere are formed on the heating of a dilute aqueous solution of K₂[Ru(NO)Cl₅] with pyridine. The evaporation of the reaction solution with concentrated hydrochloric acid gives fac-[Ru(NO)(Py)₂Cl₃] (I) in a yield of ~90%. The structures of two crystalline modifications of this complex are determined by X-ray diffraction analysis (CIF files ССDС nos. 1452208 (Ia) and 1452207 (Ib)). IR spectroscopy shows that the irradiation of complex I (λ ~ 450 nm, T = 80 K) results in photoisomerization with the formation of the metastable state MS1 in which the nitroso group is coordinated by the oxygen atom. The activation parameters of the photoisomerization are determined from the data of differential scanning calorimetry (DSC). Compound trans-[Ru(NO)Py₄(OH)]Cl₂ ? H₂O is isolated in a yield of ~70% on reflux of complex I with a pyridine excess in an aqueous solution, and the presence of molecules of water of crystallization in this compound is confirmed by thermal gravimetry (TG) and IR spectroscopy.

Full text of DOI:10.1134/S1070328416120046

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2016, Vol. 42, No. 12, pp. 768–774. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.N. Makhinya, M.A. Il’in, R.D. Yamaletdinov, I.A. Baidina, S.V. Tkachev, A.P. Zubareva, I.V. Korol’kov, D.A. Piryazev, 2016, published in Koordi-
natsionnaya Khimiya, 2016, Vol. 42, No. 12, pp. 741–746.
Synthesis, Some Properties, and Crystalline Modifications
of fac-[Ru(NO)(Py)2Cl3]
A. N. Makhinyaa, b, *, M. A. Il’ina, b, R. D. Yamaletdinova, I. A. Baidinaa, S. V. Tkacheva,
A. P. Zubarevaa, I. V. Korol’kova, b, and D. A. Piryazeva, b
aNikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
bNovosibirsk State University, Novosibirsk, 630090 Russia
*e-mail: sas.fen@mail.ru
Received March 18, 2016
Abstract⎯According to the data of 1H NMR spectroscopy, trans-hydroxochloro complexes containing from
two to four pyridine molecules in the internal sphere are formed on the heating of a dilute aqueous solution
of K2[Ru(NO)Cl5] with pyridine. The evaporation of the reaction solution with concentrated hydrochloric
acid gives fac-[Ru(NO)(Py)2Cl3] (I) in a yield of ~90%. The structures of two crystalline modifications of
this complex are determined by X-ray diffraction analysis (CIF files ССDС nos. 1452208 (Ia) and 1452207
(Ib)). IR spectroscopy shows that the irradiation of complex I (λ ~ 450 nm, T = 80 K) results in photoisom-
erization with the formation of the metastable state MS1 in which the nitroso group is coordinated by the oxy-
gen atom. The activation parameters of the photoisomerization are determined from the data of differential
scanning calorimetry (DSC). Compound trans-[Ru(NO)Py4(OH)]Cl2 ⋅ H2O is isolated in a yield of ~70%
on reflux of complex I with a pyridine excess in an aqueous solution, and the presence of molecules of water
of crystallization in this compound is confirmed by thermal gravimetry (TG) and IR spectroscopy.
Keywords: ruthenium nitrosyl, amino complexes, chloro complexes, pyridine, X-ray diffraction analysis,
1H NMR spectroscopy, IR spectroscopy, thermogravimetry, photoisomerization, differential scanning cal-
orimetry
DOI: 10.1134/S1070328416120046
INTRODUCTION
dinitrotetrapyridine complex with chloric [10, 11] or
trifluoroacetic [12] acids as follows:
Ruthenium nitroso complexes are actual objects of
the study of modern coordination chemistry due to
several reasons. First, these compounds are biologi-
cally active and considered as additional sources and
low-toxicity regulators of the nitrogen monoxide con-
centration in biological systems [1, 2].
Second, the photochemical transformations of the
ruthenium nitroso complexes [3, 4] give prospects for
the synthesis of hybrid materials based on them and
combining the photochromic properties with electric
conductivity or magnetism [5, 6]. Among the pres-
ently known nitrosoruthenium compounds, the pyri-
dine complexes [Ru(NO)(Py)4Cl](PF6)2 ⋅ 0.5H2O [7,
8] and [Ru(NO)(Py)2(NO2)2(OH)] [9] are character-
ized by the highest populations of the photogenerated
metastable states. Published data on the studies of the
photoisomerization of other pyridine complexes of
nitrosoruthenium are lacking.
trans-[Ru(Py)4(NO2)2] + 2H+
→ trans-[Ru(NO)(Py)4(OH)]2+
+ 1/2H2O + 1/2NO + 1/2NO2.
–
–
Only compounds with
and
anions in
PF6
ClO4
the external sphere can be isolated in high yields (70–
85%) in the solid phase from aqueous solutions, and
the structure of the compound with
–
was deter-
PF6
mined by X-ray diffraction analysis [13]. The chloride
salt can be obtained only by the reaction of
[Ru(Py)4(NO2)2] with trifluoroacetic acid in acetoni-
trile followed by the precipitation of the product with
tetrabutylammonium chloride [12].
This work is the continuation of our studies [14]
devoted to the search for synthesis procedures and the
establishment of the structures of the ruthenium
nitroso complexes with coordinated pyridine mole-
cules. The purpose of this work is the development of
procedures for the synthesis of compounds I and
Data on the synthesis and structure of fac-
[Ru(NO)Py2Cl3] (I) are scarce. Compounds contain-
ing the trans-[Ru(NO)Py4(OH)]2+ complex cation trans-[Ru(NO)Py4(OH)]Cl2 ⋅ H2O (II) in high yields,
can be obtained by the reaction of the ruthenium(II) spectral characterization of these compounds, estab-
768

SYNTHESIS, SOME PROPERTIES, AND CRYSTALLINE MODIFICATIONS
769
IR, ν, cm–1: 3440, 3350, 3150 ν(OH); 3100–3000
ν(CH); 1848 ν(NO); 1635 δ(HOH); 1607, 1570, 1485,
1449, 1360 ν(Carom–Carom), ν(Carom–Narom); 1215,
1153, 1067, 1015 δ(CHsh); 949, 885 δ(RuOH); 783,
768, 696, 660, 642 δ(CHout-of-plane); 596 ν(Ru–NNO),
δ(RuNO); 565 ν(Ru–OOH); 463 ν(Ru–NPy); 298,
lishment of the structures of the crystalline modifica-
tions of the dipyridine complex by X-ray diffraction
analysis, and the study of its photoisomerization.
EXPERIMENTAL
287, 261, 239 δ(NPy–Ru–NPy). 1H NMR (DMSO), δ,
The starting K2[Ru(NO)Cl5] was obtained from
commercially available ruthenium trichloride hydrate
using a described procedure [15]. Other reagents and
solvents were used as received (all of them were not
lower than reagent grade).
ppm: 9.08 d (8H, H2,6), 8.79 t (4H, H4), 8.25 t (8H,
1
H3,5). H NMR (H2O), δ, ppm: 8.45 d (8H, H2,6),
8.17 t (4H, H4), 7.67 t (8H, H3,5), 6.99 (1H, OH).
Synthesis of complex I. A weighed sample (2.0 g,
5.2 × 10–3 mol) of K2[Ru(NO)Cl5] was placed in a
beaker and dissolved in ~1 L of distilled water, and
pyridine (~5 mL) was added. The beaker was covered
with a watch glass, and the reaction mixture was boiled
for ~20 min. The obtained solution was evaporated on
a rotary evaporator to wet salts. Concentrated hydro-
chloric acid (~10 mL) was added to the obtained mix-
ture, and the resulting mixture was evaporated to dry-
ness. The procedure of evaporation with the acid was
repeated once more. Then distilled water (~10 mL)
was added to dissolve KCl, and a red product was fil-
tered off on a glass porous filter (40 pores). The pre-
cipitate was washed with cold water (~5 mL), ethanol,
and ether. The yield of compound I was ~90%.
For C20H23N5O3Cl2Ru
anal. calcd., %: C, 43.41; Н, 4.19; N, 12.65; Cl, 12.81.
Found, %:
C, 41.5; Н, 4.4;
N, 12.1; Cl, 12.7.
The IR spectra of the samples in KBr pellets were
recorded on a Scimitar FTS 2000 FT-IR spectrometer
in a range of 4000–375 cm–1 and on a Vertex 80 FT-IR
spectrometer in the range 600–80 cm–1. To detect
photoisomerization, the substance as pellets with KBr
was irradiated with a laser (450 nm, 100 mW) for
10 min and then the IR spectrum was rapidly
recorded.
Analyses to C, H, and N were carried out on a
EURO EA3000 analyzer, and Cl was analyzed using
the Scheniger volumetric method with preliminary
burning in oxygen [16].
The 1H NMR spectra of solutions of the complexes
were recorded on a Bruker Avance III spectrometer at
a frequency of 500.0 MHz.
Single crystals of compound Ia suitable for X-ray
diffraction analysis were obtained by the slow evapora-
tion of a solution of compound I in DMF, and single
crystals of compound Ib were obtained similarly from
a saturated aqueous solution.
IR, ν, cm–1: 3110–3030 ν(CH); 1867 ν(NO); 1606,
1482, 1449, 1352 ν(Carom–Carom), ν(Carom–Narom);
1241, 1209, 1156, 1093, 1066, 1018 δ(CHsh); 756, 689,
648 δ(CHout-of-plane); 605, 600 ν(Ru–NNO), δ(RuNO);
449 ν(Ru–NPy); 343, 329, 315 ν(Ru–Cl); 252, 222
Thermogravimetry (TG) was carried out on a TG
209 F1 Iris® thermobalance (NETZSCH) (heating
rate 10 K/min in a helium flow, helium flow rate
30 mL/min, Al2O3 crucible, weighed sample ~10 mg).
The experimental results were processed using the
OriginPro program package [17].
A NETZSCH DSC 204 F1 Phoenix differential
scanning calorimeter was used to determine the
kinetic parameters of the backward isomerization of
the MS1 metastable state. A weighed sample (1–3 mg)
was placed in an aluminum boat, cooled in nitrogen
vapors, irradiated with a laser (450 nm, 100 mW) for
10 min, and rapidly transferred to the preliminarily
cooled calorimeter. The samples were heated at differ-
ent rates (12 and 15 K/min) in an argon flow
(25 mL/min). The calorimeter was calibrated by the
melting of standard samples (C6H12, Hg, KNO3, In),
and the experimental data were processed in the
Netzsch Proteus Analysis program package [18].
δ(NPy–Ru–NPy). 1H NMR (DMSO), δ, ppm: 9.21 d
(4H, H2,6), 8.72 t (2H, H4), 8.23 t (4H, H3,5).
For C10H10N3OCl3Ru
anal. calcd., %: C, 30.36; Н, 2.55; N, 10.62; Cl, 26.88.
Found, %:
C, 30.3; Н, 2.9; N, 10.5; Cl, 26.9.
Synthesis of complex II. Distilled water (~600 mL)
and an excess of pyridine (~30 mL) were added to a
weighed sample (~2.0 g, 5.1 × 10–3 mol) of prelimi-
narily grinded compound I. The reaction mixture was
refluxed for ~10 min. The obtained yellow solution
was evaporated on a rotary evaporator to a red-orange
oily residue (~5 mL), which was transferred to a bea-
ker with the addition of ethanol (~20 mL). An ethan-
olic solution was evaporated at room temperature to
The X-ray phase analysis of the grinded crystals
was carried out on a DRON-3M diffractometer (R =
192 mm, CuKα radiation, Ni filter, scintillation detec-
~5 mL, and a threefold volume of THF was added. tor with amplitude discrimination). The samples were
After 10–15 min, a bright yellow precipitate that deposited as thin layers on the smooth side of a stan-
formed was filtered off. The yield of compound II was dard quartz cell. The diffraction patterns of the com-
~70%.
pounds were completely indexed by the data of single-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 42 No. 12 2016

770
MAKHINYA et al.
Table 1. Crystallographic data and the experimental and refinement parameters for the structures of compounds Ia and Ib
Value
Parameter
Ia
Ib
FW
395.63
Monoclinic
P21/c
395.63
Monoclinic
P21/c
Crystal system
Space group
a, Å
15.4631(7)
6.8609(3)
14.5966(6)
116.473(2)
1386.19(10)
8.006(2)
12.758(3)
14.308(3)
98.810(13)
1444.1(6)
b, Å
c, Å
β, deg
V, Å3
Z
4
4
calcd, g/cm3
1.896
1.820
ρ
μ, mm–1
1.699
1.631
F(000)
776
776
Crystal size, mm
θ Range, deg
0.25 × 0.20 × 0.18
2.79–33.34
0.18 × 0.15 × 0.10
2.88–30.38
Ranges of reflection indices
–10 ≤ h ≤ 18,
–10 ≤ k ≤ 3,
–10 ≤ l ≤ 18
–11 ≤ h ≤ 8,
–17 ≤ k ≤ 18,
–20 ≤ l ≤ 16
Number of measured reflections
Number of independent reflections
Rint
2508
2203
15766
4331
0.0126
0.0329
Completeness of data collection, %
Number of refined parameters
52.1 (θ = 25.25)
164
99.8 (θ = 25.25)
173
GOOF on F2
1.078
1.039
R factor (I > 2σ(I))
R factor (over all data)
Δρmax/Δρmin, e Å–3
R1 = 0.0312, wR2 = 0.0845
R1 = 0.0385, wR2 = 0.0875
0.614/–0.556
R1 = 0.0303, wR2 = 0.0658
R1 = 0.0467, wR2 = 0.0695
0.531/–0.307
crystal studies, which confirmed that the isolated bridge Crystallographic Data Centre (CIF files
products were single-phase.
nos. 1452208 and 1452207, respectively; www.ccdc.
cam.ac.uk/data_request/cif).
X-ray diffraction analysis. Unit cell parameters
were determined and a set of experimental intensities
was obtained on an X8 APEX Bruker automated dif-
fractometer (MoKα radiation, graphite monochroma-
tor, two-coordinate CCD detector). The structures
were solved by the heavy atom method and refined in
the anisotropic approximation of non-hydrogen
atoms. Hydrogen atoms were specified geometrically
in the idealized positions. All calculations were per-
formed using the SHELX-97 program package [19].
RESULTS AND DISCUSSION
Attempts to obtain the ruthenium nitrosopyridine
complexes by the reaction of K2[Ru(NO)Cl5] with an
excess of pyridine in the absence of any solvent were
unsuccessful: no visible changes occurred either at
room temperature or on prolonged reflux.
The [Ru(NO)Cl5]2– ion is activated in an aqueous
solution on heating, and the chloroaqua complexes
The crystallographic characteristics and the main
exhibit weakly acidic properties [15, 20]. According to
refinement parameters for compounds Ia and Ib are
1
presented in Table 1. The data on the structures of the data of H NMR spectroscopy, the formation of
compounds Ia and Ib were deposited with the Cam- the pyridine complexes in the reaction of a dilute solu-
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SYNTHESIS, SOME PROPERTIES, AND CRYSTALLINE MODIFICATIONS
771
tion of K2[Ru(NO)Cl5] with an excess of pyridine is 15 min of reflux. The subsequent evaporation of the
observed already 5 min after the beginning of heating, reaction solution in the presence of an excess of chlo-
and
the
concentration
of
the
trans-
ride ions in an acidic medium results in the formation
of compound I
[Ru(NO)Py4(OH)]2+ form becomes maximum in 10–
2+
+
NO
NO
Ru
NO
Py
Py
Cl
Cl
Py
Py
Py
Py
Py
Py
Cl
Py
KCl
KCl, HCl
T, °C
Ru
Cl
(I)
Ru
T, °C
.
OH
OH
This scheme is also confirmed by the fact that com- nium(II) nitroso complexes [25–27] and bands of low,
pound mer-[Ru(NO)Py3Cl(OH)]Cl ⋅ 1.5H2O, whose medium, and high intensity caused by the presence of
the coordinated pyridine molecules [28, 29]. In addi-
tion, the spectrum of compound II contains medium-
and low-intensity bands of stretching vibrations of
water molecules in a range of 3440–3150 cm–1.
structure was determined by X-ray diffraction analysis
[21], was isolated earlier from a similar system.
The evaporation of the reaction solution obtained
by the reaction of K2[Ru(NO)Cl5] with a pyridine
excess affords compound II in a yield lower than 30%.
Probably, such a low yield is due to the occurrence of
the above mentioned processes of the substitution of
the coordinated pyridine molecules by chloride ions
and the formation of polymer species with bridging
hydroxide ions [22, 23]. As it turned out, it is more
efficient to use complex I as the initial ruthenium-
containing compound for the synthesis of complex II.
The presence of molecules of water of crystalliza-
tion in tetrapyridine complex II is also confirmed by
the data of TG analysis (Fig. 1) carried out in a helium
atmosphere. One molecule of water of crystallization
is removed (a value of 3.2% was both calculated and
found from the mass loss curve) on the heating of
compound II to ~110°C. The further heating to
~170°C results in the detachment of two pyridine mol-
ecules (calculated: 28.6%, found from the TG curve:
27.7%) and affords trans-[Ru(NO)(Py)2Cl2(OH)] as
an intermediate. The subsequent thermolysis
stages are poorly separated, and the final thermolysis
product contains, according to the X-ray phase analy-
sis data, metallic ruthenium and a phase amorphous to
X-rays (probably, carbon).
The 1H NMR spectra of solutions of compounds I
and II exhibit three groups of signals assigned to three
1
types of H nuclei in the ortho, para, and meta posi-
tions of the coordinated pyridine molecules. The val-
ues of δ(1Н) range from 7 to 10 ppm, which is a char-
acteristic range for the pyridine complexes of nitro-
soruthenium [10, 24].
The IR spectra of the obtained compounds contain
intense bands of ν(NO) stretching vibrations in the
range characteristic of the most part of the ruthe-
Dipyridine complex I was crystallized from differ-
ent solvents as crystalline modifications Ia (from
DMF) and Ib (from water). The structure of the fac-
[Ru(NO)(Py)2Cl3] complex species with the numera-
tion of atoms and thermal vibration ellipsoids is pre-
sented in Fig. 2. Selected interatomic distances and
angles are given in Table 2.
100
ТG
90
80
70
Two pyridine molecules in the complex species are
arranged in the cis position to each other, and the
square environment in the equatorial plane is supple-
mented by two chloride ions. The average values of
similar bond lengths in species Ib are much higher
than those in Ia except for Ru(1)–N and Ru(1)–
Cl(1). The most differences in interatomic distances
are observed along the O–N–Ru(1)–Cl(3) axis. On
going from Ib to Ia, the contraction along this axis is
~0.07 Å, the sum of interatomic distances along the
N(1)–Ru(1)–Cl(2) axis decreases by ~0.03 Å, and
that along the N(2)–Ru(1)–Cl(1) axis remains
unchanged. The Ru–N(Py), Ru–Cl, Ru–N(NO),
and N–O distances in these crystalline modifications
are characteristic of the known ruthenium nitroso
complexes [30–32].
60
50
40
30
20
10
0
DTG
DTA
100
200
300
400
500
Temperature, °С
Fig. 1. TG curves for trans-[Ru(NO)Py (OH)]Cl ⋅ H O.
4
2
2
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 42 No. 12 2016

772
MAKHINYA et al.
60
O
2
1
N
Cl(1)
N(1)
Cl(2)
1730
ν
(MS1)
NO
40
Ru(1)
N(2)
C(15)
C(14)
C(25)
C(24)
20
0
Cl(3)
C(11)
C(21)
1867
C(22)
ν
(GS)
NO
C(13)
C(12)
C(23)
1700 1750 1800 1850 1900 1950 2000
Wave number, cm–1
Fig. 2. Structure of the fac-[Ru(NO)Py Cl ] complex spe-
2
3
cies.
Fig. 3. IR spectra of fac-[Ru(NO)Py Cl ]: (1) in the
2 3
ground state (GS) and (2) after irradiation (GS + MS1) in
the range of ν(NO) stretching vibrations.
The coordination polyhedron of the ruthenium
atom is a slightly distorted octahedron RuN3Сl3. The
deviations of the bond angles at the ruthenium atom
from 90° do not exceed 2.7° in Ia and 3.8° in Ib. The
ONRu(1) bond angle in both structures is close to
180°. The pyridine molecules are inclined to the equa-
All curves were calculated in a range of 178–218 K,
and Ea and k0 were found to be 62.5(7) kJ/mol and
4.7(8) × 1014 s–1, respectively. Using these data, one
can calculate the maximum decomposition tempera-
torial plane at angles of 45°–55° in Ia and 40°–45° in ture (Td) of MS1, which is determined at a reaction
rate constant of 10–3 s–1 [33]. For the studied com-
Ib. The central atom in the complex species is shifted
from the equatorial plane to the NO group by 0.05 Å in
Ia and 0.07 Å in Ib.
pound, Td = 185 K.
Thus, it was established that dipyridine complex I
can be isolated in a high yield (~90%) from the reac-
tion mixture obtained by the reaction of an aqueous
Both variants of the structure of compound I are of
the insular type. They contain short C–H⋅⋅⋅Cl con-
…
tacts (Cl Н(Py) ~2.8 Å). The shortest Ru⋅⋅⋅Ru dis-
tances in the structures of compounds Ia and Ib are
~6.7 and ~6.9 Å, respectively.
exo
12 К/min
15 К/min
0.10
0.08
0.06
0.04
0.02
0
The photochemical transformations that occurred
under the irradiation of the polycrystalline sample of
compound I were studied by IR spectroscopy and
DSC. An additional band at 1730 cm–1, which can be
interpreted as ν(NO) for the MS1 state [8, 9], appears
in the IR spectrum of the irradiated sample (Fig. 3).
The DSC method was used to study the kinetics of
the backward isomerization of the MS1 state. The
measurements were carried out for three different
weighed samples at different heating rates. The
obtained temperature dependence of the heat flow
(Fig. 4) is approximated by the first-order kinetic
equation
T
Ea
kBT
⎛
⎞
−
Ea k0
′
ꢀ
⎜
⎟
H = Htotk0 exp −
−
e
dT ,
∫
T0
⎜ kBT
q
⎟
⎠
⎝
–95
–85
–75
–65
–55
where
is the heat flow, Htot is the total effect, k0 is
H
Temperature, °С
the preexponential factor, Ea is the activation energy, q
is the heating rate, kВ is the Boltzmann constant, and
T0 is the initial temperature.
Fig. 4. Calculated (solid lines) and experimental (points)
DSC data for irradiated fac-[Ru(NO)Py Cl ].
2
3
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SYNTHESIS, SOME PROPERTIES, AND CRYSTALLINE MODIFICATIONS
773
Table 2. Selected interatomic distances and angles in the structures of compounds Ia and Ib
d, Å
Bond
Ia
Ib
Ru(1)–N
1.784(3)
1.766(2)
Ru(1)–N(1)
Ru(1)–N(2)
Ru(1)–Cl(1)
Ru(1)–Cl(2)
Ru(1)–Cl(3)
N–O
2.108(3)
2.1238(16)
2.1195(17)
2.3778(7)
2.3782(7)
2.3415(8)
1.115(3)
2.111(3)
2.3848(11)
2.3586(10)
2.3038(10)
1.062(4)
ω, deg
Angle
Ia
Ib
NRu(1)N(1)
92.68(13)
92.29(15)
90.38(13)
89.92(11)
177.93(10)
90.38(13)
88.73(7)
177.22(7)
89.25(8)
89.21(12)
91.05(4)
93.79(8)
92.41(8)
89.98(7)
89.74(7)
178.55(7)
89.27(5)
87.13(5)
177.61(5)
88.71(5)
90.63(6)
90.31(3)
88.90(3)
89.34(3)
176.45(5)
89.65(5)
176.8(2)
NRu(1)N(2)
NRu(1)Cl(1)
NRu(1)Cl(2)
NRu(1)Cl(3)
N(1)Ru(1)Cl(1)
N(1)Ru(1)Cl(3)
N(2)Ru(1)Cl(1)
N(2)Ru(1)Cl(3)
N(2)Ru(1)N(1)
Cl(1)Ru(1)Cl(2)
Cl(1)Ru(1)Cl(3)
Cl(2)Ru(1)Cl(3)
Cl(2)Ru(1)N(1)
Cl(2)Ru(1)N(2)
ONRu(1)
88.10(4)
88.70(4)
177.24(8)
89.75(8)
176.6(4)
solution of K2[Ru(NO)Cl5] diluted with respect to
ruthenium with a pyridine excess. To obtain tetrapyri-
dine complex II, it is more efficient to use complex I
instead of K2[Ru(NO)Cl5] as the starting ruthenium-
containing reagent. The formation of the isonitrosyl
state Ru–O–N (MS1) was detected and the kinetic
parameters of this isomerization were determined in
the course of the photochemical studies carried out for
compound I.
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