Synthesis and crystal structure of a novel ruthenium(II) complex with in situ generated dithiobiurea ligand

Accepted Manuscript Synthesis and crystal structure of a novel ruthenium(II) complex with in situ generated dithiobiurea ligand Ana I. Matesanz, Carolina Hernández, Josefina Perles, Pilar Souza PII:

S0022-328X(15)30249-7

DOI:

10.1016/j.jorganchem.2015.12.035

Reference:

JOM 19341

To appear in:

Journal of Organometallic Chemistry

Received Date: 28 October 2015 Revised Date:

15 December 2015

Accepted Date: 21 December 2015

Please cite this article as: A.I. Matesanz, C. Hernández, J. Perles, P. Souza, Synthesis and crystal structure of a novel ruthenium(II) complex with in situ generated dithiobiurea ligand, Journal of Organometallic Chemistry (2016), doi: 10.1016/j.jorganchem.2015.12.035. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Synthesis and crystal structure of a novel ruthenium(II) complex with in

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situ generated dithiobiurea ligand

Ana I. Matesanz,a* Carolina Hernández,a,b Josefina Perlesc and Pilar Souzaa a

Departamento de Química Inorgánica (M-07), Facultad de Ciencias, c/ Francisco Tomás y

b

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Valiente nº 7, Universidad Autónoma de Madrid, 28049-Madrid, Spain.

Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Ciencias del

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Medio Ambiente, Avd. Carlos III s/n, Universidad de Castilla-La Mancha, 45071-Toledo, Spain. c

Servicio Interdepartamental de Apoyo a la Investigación (M-13), Facultad de Ciencias, c/

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Francisco Tomás y Valiente nº 7, Universidad Autónoma de Madrid, 28049-Madrid, Spain

Keywords: 2,5-Dithiobiurea / Ruthenium / Thiosemicarbazone transformation / X-Ray diffraction / [NSS]-donor set

*

Corresponding author. Tel.: +34 914973868; fax: +34 914974833. E-mail: [email protected] 1

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Abstract Upon reaction with RuCl2(PPh3)3 in toluene in presence of triethylamine, 2,6diacetylpyridine mono(4-methoxyphenyl thiosemicarbazone) undergoes an unusual and

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interesting chemical transformation leading to the formation of a dithiobiurea ruthenium(II) complex. The new complex was characterized by analytical, spectroscopic and single crystal X-ray diffraction techniques. The crystallographic study confirmed the presence of

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1,6-(4-metoxyphenyl)-2,5-dithiobiurea acting as monoanionic SNS tridentate ligand. Thus the coordination geometry around the ruthenium(II) ion is a distorted octahedral where the

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SNS donor set of the ligand and one co-ordinated chlorido constitute the equatorial plane.

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The remaining apical coordination positions are filled up by two triphenylphosphines.

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1. Introduction The chemistry of organometallic and coordination ruthenium complexes has raised interest in latest decades because of their great deal applications in various fields such as

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catalysis,[1,2] photochemistry and photophysics[3-7] and more recently, in supramolecular[8and bioinorganic chemistry.[11-19] Clear correlations can be observed between their

properties and the nature of the ligands bound to the ruthenium center. In particular, mixed

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hard-soft nitrogen–sulfur ruthenium complexes have been widely investigated because of their properties and usefulness in catalysis and chemotherapy.[20-23]

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Thiosemicarbazones (R1R2C=N-NH-C(S)-NR3R4) are an important and versatile type of nitrogen-sulfur ligands because their highly interesting chemical and biological properties.[24-28] As a part of our systematic investigation directed towards synthesis and characterization

of

platinum

group

metal

complexes

bearing

α-N-heterocyclic

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thiosemicarbazones we have isolated and structurally characterized a series of new metal compounds with a variety of interesting features such mononuclear/polynuclear nature or chelate/cyclometallate behavior. [29-34]

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Recently we undertook the synthesis of the new ligand 2,6- diacetylpyridine mono(4-methoxyphenylthiosemicarbazone) and its palladium(II) derivative. Structural

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study revealed the mononuclear neutral nature of the cyclometallated derivative and the dianionic [CNS] tridentate behavior of the ligand. [35] To extend the knowledge in this research field, we undertook the reactivity study of 2,6diacetylpyridine

mono(4-methoxyphenylthiosemicarbazone)

ligand,

HL1,

toward

ruthenium(II) salts. However, during the course of our investigations we came across a very interesting phenomenon: under reaction conditions the thiosemicarbazone ligand is

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transformed into a new dithiobiurea one. As well as cyclization reactions are rather common in thiosemicarbazone chemistry the formation of dithiobiurea has been rarely observed.[36,37]

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Herein we report the synthesis and structural characterization of an unexpected novel ruthenium(II) complex, [RuClL2(PPh3)2], in which the L2 is the dianion of the in situ generated 1,6-(4-methoxyphenyl)-2,5-dithiobiurea ligand (Scheme 1).

OCH3

N H

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H N

S H N N H S

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OCH3

H2L2

2. Experimental

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Scheme 1.

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2.1. Physical Measurements

Elemental analyses were performed on a LECO CHNS-932 microanalyzer. Matrix

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assisted laser desorption/ionization (MALDI) mass spectrum were performed on a BRUKER UltraflexIII spectrometer with DCTB (trans-2-[3-(4-tert-butylphenyl)-2-methyl2-propenyli-dene]-malononitrile) matrix. 1H NMR spectrum (DMSO-d6) was recorded on BRUKER AMX-300 spectrometer. All cited measurements were obtained out by the Servicio Interdepartamental de Investigación (SIDI) of the Universidad Autónoma de Madrid.

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Melting points were determined with a Stuart Scientific SMP3 apparatus. Infrared spectra (KBr pellets) were recorded on a Bomen–Michelson spectrophotometer (4000–400

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cm-1). Magnetic susceptibility was measured using a Sherwood Scientific balance. 2.2. Materials

Solvents were purified and dried according to standard procedures. Hydrazine

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hydrate, 2,6-diacetylpyridine, 4-methoxyphenyl isothiocyanate, RuCl2(PPh3)3 were commercially available.

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2.3. Synthesis of [RuClL2(PPh3)2]

Method 1. The reaction of 2,6-diacetylpyridine mono(4-methoxyphenylthiosemicarbazone) ligand, HL1, prepared as described in reference 35g, with RuCl2(PPh3)2 in 1:1 M ratios was carried out, in presence of Et3N, in degassed toluene for 3 h at room temperature under nitrogen atmosphere. The resulting brown solution was filtered and evaporated to dryness.

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The solid residue was washed with pentane and dried in vacuo. Further purification by The characterization of the isolated solid failed however recrystallization from DMSO led to single crystals which were studied by X-ray diffraction techniques.

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Method 2. Then, in In order to develop a reproducible procedure, the compound was

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prepared from 1,6-(4-metoxyphenyl)-2,5-dithiobiurea, H2L2, and RuCl2(PPh3)2 following the reaction conditions above described. Yield (40%), mp 114 ºC. Elemental analysis found, C, 65.43; H, 4.92, N, 4.25; S, 4.48; C52H47N4ClO2P2S2Ru·PPh3 requires C, 65.39; H, 4.90, N, 4.35; S, 4.98 %. IR (KBr pellet): n/cm-1 3239 (s, NH); 1605 (s, thioamide I: δNH+υC=N); 913 (vw, thioamide IV: υC=S). Recrystallization from DMSO led to the isolation of brown crystals that were suitable for single crystal X-ray-diffraction and their analysis revealed that the compound displayed the 5

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same structure than the crystal obtained from method 1, with a slightly higher degree of disorder. Synthesis of 1,6-(4-metoxyphenyl)-2,5-dithiobiurea, H2L2

2.4.

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Could be prepared by direct reaction in absence of RuCl2(PPh3)2 as described below. An ethanolic solution of 4-methoxyphenylthiosemicarbazide was added dropwise with constant stirring to an ethanolic solution of 4-methoxyphenylisothiocyanate. The

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reaction mixture was stirred for one more hour and then the white solid formed was filtered, washed with cold ethanol and diethyl ether, dried in vacuo in vacuo and recrystallized from

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ethanol.

Yield (85%), mp >225 ºC. Elemental analysis found, C, 52.90; H, 5.10, N, 15.45; S, 17.45; C16H18N4O2S2 requires C, 53.05; H, 5.00, N, 15.45; S, 17.70 %. MS (MALDI with DCTB matrix) m/z 363 for [M+H]+. IR (KBr pellet): n/cm-1 3213, 3113 (s, υNH); 1607 (s,

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thioamide I: δNH+υC=N); 925 (m, thioamide IV: υC=S). 1H NMR (300 MHz, d6-DMSO, ppm), δ=9.71, 9.54 [s, NH, 1H]; 7.39, 7.36 (d, aromatic-CH, 2H); 3.75 (s, aliphatic-CH, 3H).

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C NMR (75.4 MHz, CDCl3, ppm), δ=207.00 (C=S); 154.08, 137.34, 124.40 and

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115.24 (CH-phenyl); 30.98 (-OCH3).

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2.5. Crystallography

Data were collected on a Bruker Kappa Apex II diffractometer. Crystallographic

data and selected interatomic distances and angles are listed in Tables 1 and 2. The software package SHELXTL was used for space group determination, structure solution, and refinement [24]. The structure was solved by direct methods, completed with difference Fourier syntheses, and refined with anisotropic displacement parameters.

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The crystal structure shows two different dispositions of the ligand randomly located, where the coordinated nitrogen atom is either N(2B) (41% of the molecules) or

could be located and they could not be anisotropically refined.

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N(3A) (59%). Solvent DMSO molecules are highly disordered: only not hydrogen atoms

Data collection and structural details can be found in the supplementary material. CCDC 1417568 contains the crystallographic data. These data can be obtained free of at

www.ccdc.cam.ac.uk/conts/retrieving.html

[or

from

the

Cambridge

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charge

Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44-

3. Results and Discussion 3.1. Synthesis and structure

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1223/336-033; e-mail: [email protected]].

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The reaction of 2,6-diacetylpyridine mono(4-methoxy phenylthiosemicarbazone) ligand, HL1, with RuCl2(PPh3)3 in presence of triethylamine, under nitrogen atmosphere led to the isolation of a black solid. Preliminary characterization data failed to indicate any

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unambiguous formulation for the isolated compound. Further recrystallization from DMSO led to the isolation of good quality single crystals which were studied by X-ray diffraction

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techniques.

The structural analysis allowed us to identify a new ruthenium(II) complex,

[RuClL2(PPh3)2],

in

which

the

2,6-diacetylpyridine

mono(4-methoxyphenyl

thiosemicarbazone) had undergone an unexpected chemical transformation. The molecular structure of neutral complex, which crystallized with one and two thirds of DMSO molecules in the triclinic P-1 space group, together with the ligand and coordination

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environment atom labelling scheme is shown in Fig. 1. Crystallographic data are given in

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Table 1.

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Figure 1. Molecular structure of ruthenium(II) complex [RuClL2(PPh3)2].

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Table 1. Crystal data and structure refinement for [RuClL2(PPh3)2]. C55.32H46ClN4O3.66P2Rus3.66 Chemical formula 1141.16 Formula weight 110(2) K Temperature 0.71073 Å Wavelength 0.02 x 0.07 x 0.20 mm Crystal size clear dark orange-brown plate Crystal habit triclinic Crystal system P-1 Space group a =13.1806(7) Å α = 92.734(3)° b = 14.2491(7) Å Unit cell dimensions β = 105.965(3)° c = 15.8264(7) Å Å γ = 107.292(3)° 2701.3(2) Å3 Volume 2 Z 1.403 Mg·cm-3 Density (calculated) 0.588 mm-1 Absorption coefficient 1.35 to 25.41º Theta range for data collection -15 ≤ h ≤ 15 -17 ≤ k ≤ 17 Index ranges -19 ≤ l ≤ 19 42701 Reflections collected 9904[R(int)=0.0778] Independent reflections 99.6% Coverage of independent reflections 9904/4/618 Data/restraints/parameters 1.005 Goodness of Fit 6497 data; I>2σ(I) R1 = 0.0937, wR2 = 0.2527 Final R indices all data R1 = 0.1455, wR2 = 0.2977 3.616 and -1.560 eÅ-3 Largest diff. peak and holes

The transformed symmetrical ligand acts a monoanionic tridentate S,N,S-

donor, coordinating to the ruthenium(II) center through one of the hydrazinic nitrogen atoms (which are disordered over two sites) and the two sulfur atoms generating one typical five membered (RuNNCS) and one four membered (RuNCS) chelate rings with bite angles N(3A)-Ru(1)-S(2) of 88.2(7)º and N(3A)-Ru(1)-S(1) of 61.6(7)º respectively.

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The ruthenium(II) ion is in an octahedral environment being the forth equatorial binding site occupied by a chlorido ligand and the two axial positions by triphenylphosphine ligands. The Ru-Cl and Ru-P bond distances as well as S-Ru-S and P-

complexes with similar geometry and coordination.

[38-40]

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Ru-P bond angles, listed in Table 2, are comparable to those reported for ruthenium It is important to note that upon

coordination, the deprotonated dithiobiurea ligand is resonance stabilized showing shows

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C-S distances of 1.701(14) and 1.727(13) Å and a N-N distances of 1.23(4) Å very close to

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those of a double bond suggesting coordination of the sulfur atoms in their thione form.

Table 2. Selected bond lengths (Å) and angles (°) for [RuClL2(PPh3)2]. Bond distances (Å)

Bond angles (º)

1.403(12)

C(8)-N(1)

1.290(13)

C(8)-N(2A)

1.56(3)

N(3A)-Ru(1)-S(1)

61.6(7)

C(8)-S(2)

1.727(13)

N(3A)-Ru(1)-S(2)

88.2(7)

C(9)-N(3A)

1.46(2)

N(3A)-Ru(1)-Cl(1)

169.5(7)

C(9)-N(4)

1.329(14)

S(1)-Ru(1)-P(1)

88.96(9)

1.701(14)

S(1)-Ru(1)-P(2)

89.82(9)

1.407(13)

S(1)-Ru(1)-S(2)

149.80(14)

1.23(4)

S(1)-Ru(1)-Cl(1)

108.01(13)

Ru(1)-Cl(1)

2.461(2)

S(2)-Ru(1)-Cl(1)

102.18(12)

Ru(1)-P(1)

2.393(2)

S(2)-Ru(1)-P(1)

92.31(9)

Ru(1)-P(2)

2.399(2)

S(2)-Ru(1)-P(2)

91.38(9)

Ru(1)-S(1)

2.376(3)

P(1)-Ru(1)-P(2)

174.63(8)

Ru(1)-S(2)

2.386(3)

P(1)-Ru(1)-Cl(1)

87.34(8)

Ru(1)-N(3A)

1.890(19)

P(2)-Ru(1)-Cl(1)

88.06(9)

C(10)-N(4)

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N(2A)-N(3A)

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C(9)-S(1)

N(3A)-Ru(1)-P(1)

91.0(5)

N(3A)-Ru(1)-P(2)

93.0(5)

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C(7)-N(1)

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The formation of [RuClL2(PPh3)2] complex involves necessarily several unusual chemical

transformations

of

2,6-diacetylpyridine

mono(4-methoxyphenyl

sequences illustrated in Scheme 2 thus seem probable. CH3

N

HN

S

H3C

S

· H2O

OCH3

CH3

N

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HN

H NH2 N

O

H N N

O

O

OCH3

H2L1

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H3C

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thiosemicarbazone) ligand. Though it is not possible to provide an exact mechanism, the

NH2

NH

HN

H NH2 N 2

HN

S

RuCl2(PPh3)3

S

OCH3

N HN

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Ru S

PPh3 Cl

PPh3 OCH3

OCH3

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OCH3

PPh3

NH2

HN

Ph P H 3 N N S

OCH3

NH S

Ru Cl PPh3

RuClL2(PPh3)2

Scheme 2. Proposed formation mechanism of [RuClL2(PPh3)2]

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It is well known that the formation of a Schiff base (imine) is a reversible reaction and its conversion back (hydrolysis) to carbonyl and amine starting materials occur readily not only under aqueous acid or base catalysis or upon heating but also under metal ion

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catalysis being the rate of hydrolysis of Schiff base depending on the nature of metal ion.[41,42] Since no evidence of hydrolysis has been found for 2,6-diacetylpyridine mono(4methoxyphenyl thiosemicarbazone) ligand in the absence of metal ions, seems reasonable

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to think that is the ruthenium(II) ion who promotes the hydrolysis. Its The formation of [RuClL2(PPh3)2] complex is believed to be initiated by the hydrolysis of 2,6-

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diacetylpyridine mono(4-methoxyphenylthiosemicarbazone) and subsequent coordination with of 2,6-diacetylpyridine mono(4-methoxyphenyl thiosemicarbazide) with ruthenium(II) forming leads to an intermediate complex which contains a four membered chelate ring, the mechanism probably involves nucleophilic attack of and the unprotected terminal amino

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attacks on the thione carbon of a second thiosemicarbazone thiosemicarbazide ligand. Subsequently, a triphenylphosphine ligand can be replaced by the sulfur atom. The resulting dithiobiureido ligand remains coordinated to the ruthenium atom leading the final

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complex.

To gain further insight into this unexpected result we proposed to perform the direct

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synthesis of the new 1,6-(4-metoxyphenyl)-2,5-dithiobiurea ligand, H2L2, from 4-methoxy phenylthiosemicarbazide and 4-methoxyphenyl isothiocyanate.[413] The reaction was carried out in ethanol at room temperature and the analytical and spectroscopic data of the solid isolated support the formula given for H2L2. In a second step the new ligand was suspended in degassed toluene and reacted with RuCl2(PPh3)3 in presence of triethylamine for 3 h at room temperature under nitrogen atmosphere. The resulting brown solution was filtered and evaporated to dryness. The solid residue was washed with pentane, dissolved in 12

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dichloromethane and again evaporated to dryness. The characterization of the solid obtained, carried out by analytical, spectroscopic and single X-ray diffraction techniques,

3.2. Spectroscopic studies Magnetic

susceptibility

measurement

showed

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confirmed the formation of the expected compound, [RuClL2(PPh3)2].

that

[RuClL2(PPh3)2]

was

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diamagnetic as is expected for low spin octahedral d6 complexes. However due to the low solubility of the complex it was not possible to get 1H NMR spectrum of reasonable

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quality. The 1H NMR spectrum of the new dithiobiurea ligand shows the signals in the expected regions: two singlets at low field (9.71 and 9.54 ppm) assigned NH protons, two doublets at 7.39 and 7.36 ppm due to aromatic protons and one singlet at 3.75 ppm assignable to -OCH3 protons.

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C NMR spectrum of the free ligand shows the expected

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carbon signals supporting the 1H NMR assignments.

The most significant IR bands are listed in the Experimental Section. Although thioamides form a complex vibrational group with four characteristic bands in the 1600 -

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600 cm-1 domain, the proposed assignment is based on our previous studies of thiosemicarbazone derivatives. Due to the high delocalization Upon coordination induces

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only minor changes in thioamide I band while the thioamide IV band shifts to lower wavenumbers indicating coordination via the thioamide sulfur atoms.

Conclusions

In general, thiosemicarbazones are relatively simple to synthesize but complications can arise. As typical Schiff bases are labile toward hydrolysis, also it is well know that the condensation reaction can lead to the formation of different heterocyclic by-products and 13

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moreover a series of interesting metal mediated transformations have been described. However, to our knowledge the dithiobiurea by-product had not been isolated to the date although its formation had been proposed by M. Christlieb et al. in 2006.[37]

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We have demonstrated the formation of 1,6-(4-metoxyphenyl)-2,5-dithiobiurea from the reaction between 2,6-diacetylpyridine mono(4-methoxyphenylthiosemicarbazone) and RuCl2(PPh3)3. We have also developed a reproducible synthesis method for the

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ruthenium(II) complex formed and thus we think this may be useful for others involved in

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this chemistry.

Acknowledgements

We are grateful to Ministerio de Economía y Competitividad, Instituto de Salud Carlos III

References

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(PI1100659), of Spain for financial support.

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[1] F.B. Hamad, T. Sun, S. Xiao, F. Verpoort, Coord. Chem. Rev. 2013, 257, 2274–2292. [2] D.K. Dutta, B. Deb, Coord. Chem. Rev. 2011, 255, 1686-1712.

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[3] J. Yin, M. Velayudham, D. Bhattacharya, H. Lin, K. Lu, Coord. Chem. Rev. 2012, 256, 3008-3035.

[4] B.J. Coe, Coord. Chem. Rev. 2013, 257, 1438-1458. [5] G.C. Vougioukalakis, A.I. Philippopoulos, T. Stergiopoulos, P. Falaras, Coord. Chem. Rev. 2011, 255, 2602-2621 [6] M.J. Rose, P.K. Mascharak, Coord. Chem. Rev. 2008, 252, 2093-2114.

14

ACCEPTED MANUSCRIPT

[7] S. Campagna, F. Puntoriero, F. Nastasi, G. Bergamini, V. Balzani, Top. Curr. Chem. 2007, 280, 117-214.

[9] B. Therrien, Eur. J. Inorg. Chem. 2009, 17, 2445–2453.

RI PT

[8] K. Severin, Chem. Commun. 2006, 3859–3867.

Y. Han, W. Jia, W. Yu, G. Jin, Chem. Soc. Rev. 2009, 38, 3419-3434.

[11]

C.G. Hartinger, P.J. Dyson, Chem. Soc. Rev. 2009, 38, 391-401.

[12]

A.K. Singh, D.S. Pandey, Q. Xu, P. Braunstein, Coord. Chem. Rev. 2014, 270–271,

SC

[10]

31–56.

F. Beckford, D. Dourth, M. Shaloski Jr., J. Didion, J. Thessing, J. Woods, V.

M AN U

[13]

Crowell, N. Gerasimchuk, A. Gonzalez-Sarrías, N.P. Seeram, J. Inorg. Biochem. 2011, 105, 1019–1029. [14]

G. Sava, R. Gagliardi, M. Cocchietto, K. Clerici, I. Marrella, E. Alessio, G.

[15] [16]

TE D

Mestroni, R. Milanino, Pathol. Oncol. Res. 1998, 4, 30-36.

D. Gambino, L. Otero, Inorg. Chim. Acta 2012, 393, 103-114. M.J. Clarke, Coord. Chem. Rev. 2003, 236, 209-233. V. Brabec, O. Nováková, Drug Resistance Updates 2006, 9, 111–122.

[18]

M.G. Mendoza-Ferri, C.G. Hartinger, A.A. Nazarov, W. Kandioller, K. Severin,

EP

[17]

AC C

B.K. Keppler, Appl. Organomet. Chem. 2008, 22, 326–332.

[19] P.C.A. Bruijnincx, P.J. Sadler, Adv Inorg Chem. 2009, 7, 1–62. [20]

R. Manikandan, P. Anitha, G. Prakash, P. Vijayan, P. Viswanathamurthi, R.J.

Butcher, J.G. Malecki; J. Mol. Catal. A-Chem. 2015, 398, 312-324.

[21] R. Ramachandran, G. Prakash, S. Selvamurugan, P. Viswanathamurthi, J.G. Malecki, V. Ramkumar; Dalton Trans. 2014, 43, 7889-7902. [22] R. Mitra, A.G. Samuelson, Eur. J. Inorg. Chem. 2014, 3536–3546. 15

ACCEPTED MANUSCRIPT

[23]W. Su, Q. Qian, P. Li,X. Lei,Q. Xiao, S. Huang, C. Huang, J. Cui, Inorg. Chem. 2013, 52, 12440−12449. [24] A. Gómez-Quiroga, C. Navarro-Ranninger, Coord. Chem. Rev. 2004, 248, 119–133. J.S. Casas, M.S. García-Tasende, J. Sordo, Coord. Chem. Rev. 2000, 209, 197–261.

[26]

T.S. Lobana, R. Sharma, G. Bawa, S. Khanna, Coord. Chem. Rev. 2009, 253, 977–

RI PT

[25]

1055.

A.I. Matesanz, P. Souza, Mini Rev. Med. Chem. 2009, 9, 1389–1396.

[28]

R. Hueting, R. Tavare, J.R. Dilworth, G.E. Mullen, J. Inorg. Biochem. 2013, 128,

SC

[27]

M AN U

108-111. [29]

A.I. Matesanz, C. Pastor, P. Souza, Inorg. Chem. Comm. 2007, 10, 97–100.

[30]

A.I. Matesanz, P. Souza, J. Inorg. Biochem. 2007, 101, 245–253.

[31]

A.I. Matesanz, C. Hernández, A. Rodríguez, P. Souza, J. Inorg. Biochem. 2011,

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105, 1613–1622.

[32] A.I. Matesanz, C. Hernández, A. Rodríguez, P. Souza, Dalton Trans. 2011, 40, 57385745.

A.I. Matesanz, I. Leitao, P. Souza, J. Inorg. Biochem. 2013, 125, 26–31.

EP

[33]

[34] A.I. Matesanz, P. Souza, J. Inorg. Biochem. 2007, 101, 1354–1361.

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[35] A.I. Matesanz, C. Hernández, P. Souza, J. Organomet. Chem. 2014, 751, 374-378. [36] R. Gil-García, R. Fraile, B. Donnadieu, G. Madariaga, V. Januskaitis, J. Rovira, L. González, J. Borrás, F.J. Arnáiz, J. García-Tojal, N. J. Chem. 2013, 37, 3568-3580.

[37] M. Christlieb, H.J. Claughton, A.R. Cowley, J.M. Heslop, J.R. Dilworth, Trans. Met. Chem. 2006, 31, 88–92.

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[38] M. Adams, C. de Kock, P.J. Smith, K.M. Land, N. Liu, M. Hopper, A. Hsiao, A.R. Burgoyne, T. Stringer, M. Meyer, L. Wiesner, K. Chibale, G.S. Smith, Dalton Trans. 2015, 44, 2456-2468.

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[39] T.S. Lobana, G. Bawa, R.J. Butcher, Inorg. Chem. 2008, 47, 1488–1495.

[40] P. Paul, D.K. Seth, M.G. Richmond, S. Bhattacharya, RSC Adv. 2014, 4, 1432-1440.

International Publishers, Chichester, 2000.

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[41] R.W. Hay, Reaction Mechanisms of Metal Complexes, Horwood Publishing,

[42] S. Meghdadi, M. Amirnasr, M. Majedi, M. Bagheri, A. Amiri, S. Abbasi, K. Mereiter

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Inorg. Chim. Acta 2015, 437, 64–69.

[43] M.L. Soriano, J.T. Lenthall, K.M. Anderson, S.J. Smith, J.W. Steed, Chem. Eur. J.

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2010, 16, 10818-10831.

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ACCEPTED MANUSCRIPT Highlights A new dithiobithiourea/Ru(II) complex has been prepared and its X-ray structure determined.

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Unexpected 2,6-diacetylpyridine mono(4-methoxyphenylthiosemicarbazone) chemical transformation.

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The ligand coordinates to Ru(II) ion via SNS fashion.

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