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Cleavage of a CC bond during a solvothermal process leading to a mononuclear rhenium(III) product
Inorganic Chemistry Communications 24 (2012) 47–49
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Cleavage of a C\C bond during a solvothermal process leading to a mononuclear rhenium(III) product Andrzej Kochel a,⁎, Małgorzata Hołyńska b,⁎, Kamil Twaróg a a b
University of Wrocław, Faculty of Chemistry, F. Joliot-Curie 14, 50‐383 Wrocław, Poland Fachbereich Chemie, Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35043 Marburg, Germany
a r t i c l e
i n f o
Article history: Received 9 May 2012 Accepted 23 July 2012 Available online 29 July 2012 Keywords: Rhenium(III) Solvothermal conditions Cleavage of C\C bond
a b s t r a c t A new system is reported, where solvothermal conditions lead to a cleavage of a C\C bond in 2,2′-bipyridine-3,3′,6,6′-tetracarboxylic acid, that might be catalyzed by the starting rhenium salt, ammonium hexachloridorhenate(IV). The resulting product (1) is a rhenium(III) complex, including the applied ligand and its decomposition product in the Re3+ ion coordination sphere. 1 is characterized by X-ray diffraction, magnetic and spectroscopic, as well as TGA property measurements. © 2012 Elsevier B.V. All rights reserved.
Solvothermal synthesis in rhenium chemistry is relatively seldom represented [1]. The conditions applied during such syntheses may favor unexpected side-reactions, including catalytic processes [2]. Bond activation in solvothermal processes might lead to formation of new organic ligands, also involving C\C bond formation [3a–c]. Activating role of metal ions in such syntheses has been well investigated in the case of copper(II) ions [3d–f]. The title compound (1) was synthesized as a continuation of our project on solvothermal syntheses in rhenium coordination chemistry with the use of amine ligands, leading to compounds with unusual molecular topologies/potential radiopharmaceuticals [3g–h]. 1 is a mixed salt containing complex (2,2′-bipyridine-6, 6′-(dicarboxylic acid)-3,3′-dicarboxylato)(pyridine-2,5-dicarboxylato-N, O)chloridorhenium(III) molecules, sodium cations and chloride anions obtained in a solvothermal reaction between 2,2′-bipyridine-3,3′,6, 6′-tetracarboxylic acid and ammonium hexachloridorhenate(IV) under basic conditions. The Re3+ ion coordination sphere includes both the applied ligand, and its degradation product. Apparently a potentially catalytic process leading to a cleavage of the C\C bond joining two pyridyl rings in the 2,2′-bipyridine-3,3′,6,6′-tetracarboxylic acid takes place, involving the release of oxygen gas as a by-product. This is confirmed by control of oxygen concentration by means of an oxygen sensor (see ESI). The 2,2′-bipyridine-3,3′,6,6′-tetracarboxylate ligand (H2L1) was first introduced by Dawid et al. [4] as part of studies on design and synthesis of nitrogen/oxygen-donor ligands combined with multicarboxylic acids. Binuclear iron(II) and cobalt(II) compounds were also reported as the so far sole examples of metal complexes with ligand L1. On the other ⁎ Corresponding authors. E-mail addresses: [email protected] (A. Kochel), [email protected] (M. Hołyńska). 1387-7003/$ – see front matter © 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.inoche.2012.07.042
hand, a C\C bond cleavage catalyzed by transition metal complexes has been reported for many cases, including mainly Rh, Pd, Pt, as well as Fe, Co, Ru and Zr [5], whereas rhenium-catalyzed processes are less frequently reported [6]. The experimental procedure leading to 1 may be summarized as shown in Scheme 1. A potentially catalytic C\C bond cleavage within the ligand L 1 takes place. A rhenium(III) product is formed by reduction of the hexachloridorhenate(IV) starting compound and is isolated as crystalline material at 56% yield. The oxygen side-product is identified with the aid of an oxygen sensor (see Experimental). However, no detailed conclusions on the potentially catalytic cycles can be drawn from this study. When the analogous synthesis conditions are applied without the use of rhenium(III) starting material, no degradation of the starting carboxylic acid is observed. Coordination environment of the Re3+ ion includes one tetradentate 2,2′-bipyridine-6,6′-(dicarboxylic acid)-3,3′-dicarboxylato ligand (L1), one bidentate pyridine-2,5-dicarboxylato ligand (L2) and one chlorido ligand (Fig. 1). The Re\Clterminal bond length is of 2.344(2) Å (Table S2), which is similar as in related compounds [7]. Pyridine N12 atom of the ligand L2 is coordinated trans to the terminal chlorido ligand. L2 is also coordinated to the Re3+ ion by carboxyl O22 atom. To the best of our knowledge coordination of a non-deprotonated carboxylic group to Re3+ ion has never been reported, on the other hand, it is known for rhenium complexes at both lower and higher oxidation states [8]. The remaining four coordination places are filled with two pyridine N atoms (N1, N11) and two carboxylate O atoms (O1, O11) of the ligand L1. Thus the central Re3+ ion has coordination number 7, already reported for mononuclear rhenium(III) complexes [9]. The Re\Ocarboxyl bond lengths are at 2.022(3)–2.064(3) Å range and the Re\Npyridyl bond lengths are
48
A. Kochel et al. / Inorganic Chemistry Communications 24 (2012) 47–49
Scheme 1. General scheme for the preparation of 1.
from 2.080(3) to 2.111(4) Å, which is typical among related rhenium(III) complexes [10]. Within the ligand L1 the planes of two pyridyl rings are twisted with respect to each other by 20.6(2)° with N atoms in a cis arrangement, whereas for the free ligand the corresponding angle is of 49.87(4)° and the pyridyl N atoms are trans to each other [4]. The O11and O1-containing carboxylate group planes are twisted with respect to their parent pyridyl rings by 19.8(4) and 25.1(4)°, respectively. The corresponding twist angles for the carboxyl groups not participating in coordination to the central metal ion are 35.8(4) and 31.6(5)° for the O31- and O3-containing group, respectively. In the ligand L2 the non-coordinated O32-carboxyl group is almost coplanar with the N12-pyridyl ring, whereas the O22-coordinated carboxyl group plane is twisted with respect to the same pyridyl ring by 12.8(8)°. 1 contains also Na+ and Cl− ions. The symmetry-independent Na1 cation includes in coordination sphere two water molecules and four carboxyl/carboxylate O atoms from three independent complex molecules. Each symmetry-independent Cl− ion is involved in three O\H…Cl hydrogen bonds with one water molecule of solvation and L 1/L 2 carboxyl groups from two independent complex molecules acting as donors. Na\O coordination bonds stabilize the formation of layers in the crystal structure (Fig. 2, Table S2), governing the crystal structure, in which no significant stacking interactions between aromatic rings could
Fig. 2. One of the layers stabilized by Na\O bonds in 1, projected along [010]. C/H atoms are shown as sticks, the remaining atoms are plotted as spheres of arbitrary radii.
be found. The layers are interconnected by O\H…O and O\H…Cl type hydrogen bonds (Table S3). The new material was characterized in terms of magnetic and spectroscopic properties, as well as its thermal decomposition. Magnetic properties of 1 were investigated in the temperature range from 1.8 to 300 K under the applied magnetic field of 1 T (see Fig. 3 for χm and χmT vs. T plots). 1 shows an overall paramagnetic behavior. Spin-only magnetic momentum at room temperature is of 1.88 B.M., which corresponds to the χmT value of 0.446 cm3mol−1 K. Magnetic momentum of 1 is weakly temperature-dependent, dropping to 1.45 B.M. at 1.8 K. These values are characteristic for monomeric low-spin Re3+ ions (d 4) in Oh ligand field, which corresponds to a 3T1g ground state [11]. Electronic spectra collected for aqueous solutions of 1 are comparable to those reported for related rhenium(III) complexes and apparently dominated by MLCT bands [12] (see ESI).
Fig. 1. Molecular structure of complex 1 with atom labeling scheme. Thermal displacement ellipsoids are plotted at 30% probability level. H atoms are shown as spheres of arbitrary radii.
A. Kochel et al. / Inorganic Chemistry Communications 24 (2012) 47–49
49
0.5
0.16
0.45
0.14
0.4
0.2
-1
0.25
0.1 0.08
3
0.3
XmT [ cm mol K]
X m [cm 3 mol -1]
0.12 0.35
0.06
0.15 0.04 0.1 0.02
0.05 0 0
50
100
150
200
250
0 300
T [K] Fig. 3. χmT (dots) and χm vs. T (triangles) plots illustrating the magnetic properties of 1.
IR spectrum recorded for 1 is dominated by bands arising from the organic ligand. At 2500–3600 cm−1 broad bands assignable to νOH are observed [4]. Broad band at 1627 cm−1 can be assigned to νas(COO), whereas the bands at 1378, 1409 and 1457 cm−1 should arise from νs(COO), combined for coordinated/uncoordinated and protonated/ deprotonated carboxyl groups [4]. Weak band at 316 cm−1 on the FIR spectrum may confirm the presence of a Re\Cl bond [13]. A very strong band at 149 cm−1 with a broad shoulder reaching 300 cm−1 and weaker bands extending to lower wavenumbers may be a result of a combination of νas(Re\Cl) and δ(ClReO), δ(NReO), δ(NReN) [13]. 1, as revealed by its TGA diagram (Fig. S2), undergoes a stepwise decomposition on heating under nitrogen atmosphere. First step apparently involves release of water of solvation, combined with partial decomposition of the organic part, possibly decarboxylation of the organic ligands [14]. At about 235 °C the sample undergoes melting with further decomposition in at least two steps. Mass of the residue after the whole decomposition process may correspond to the total Na + Cl + Re content of 1. To sum up, a new system has been reported, where solvothermal conditions lead to the cleavage of the C\C bond in 2,2′-bipyridine3,3′,6,6′-tetracarboxylic acid, that might be catalyzed by the starting rhenium salt. The resulting product is a rhenium(III) complex, including the applied ligand and its decomposition product in the Re3+ ion coordination sphere, providing a new insight into the chemistry of solvothermal processes involving rhenium compounds.
(b) (c) (d) [2] (a) (b) [3] (a)
[4] [5]
[6] [7] [8]
[9]
[10]
Acknowledgments
[11]
Helpful discussions by Dr. Jarosław Sobczak and Dr. Jacek Wojaczyński are gratefully acknowledged.
[12]
[13]
Appendix A. Supplementary data Supplementary data to this article can be found online at http:// dx.doi.org/10.1016/j.inoche.2012.07.042. References [1] (a) M.N. Sokolov, N.E. Fedorova, N.V. Pervukhina, E.V. Peresypkina, A.V. Virovets, R. Petov, V.E. Fedorov, D. Fenske, Izv.Akad.Nauk SSSR,Ser.Khim.(Russ), Russ. Chem. Bull. (2006) 52;
[14]
A. Kochel, Inorg. Chem. Commun. 10 (2007) 1440; A. Kochel, M. Hołyńska, Inorg. Chem. Commun. 13 (2010) 782; R. Sevvel, T.-W. Tseng, K.-L. Lu, J. Organomet. Chem. 582 (1999) 160. S. Delgado, A. Gallego, O. Castillo, F. Zamora, Dalton Trans. 40 (2011) 847; R.H. Laye, E.J.L. McInnes, Eur. J. Inorg. Chem. 14 (2004) 2811. J. Blake, N.R. Champness, S.S.M. Chung, W.-S. Li, M. Schröder, Chem. Commun. (1997) 1675; (b) C.M. Liu, S. Gao, H.-Z. Kou, Chem. Commun. (2001) 1670; (c) Q.-H. Wei, L.-Y. Zhang, G.-Q. Yin, L.-X. Shi, Z.-N. Chen, J. Am. Chem. Soc. 126 (2004) 9940; (d) X.-M. Zhang, Coord. Chem. Rev. 249 (2005) 1201; (e) J.-P. Zhang, X.-M. Chen, Chem. Commun. (2006) 1689; (f) J.Y. Lu, B.R. Cabrera, R.-J. Wang, J. Li, Inorg. Chem. 27 (1998) 4480; (g) M.J. Clarke, M.E. Kastner, L.A. Podbielski, P.H. Fackler, J. Schreifels, G. Meinken, S.C. Srivastaval, J. Am. Chem. Soc. 110 (1988) 1818; (h) K. Liepe, J. Kropp, R. Runge, J. Kotzerke, Br. J. Cancer 89 (2003) 625. U. Dawid, F.P. Pruchnik, R. Starosta, Dalton Trans. (2009) 3348. (a) C. Perthuisot, W.D. Jones, J. Am. Chem. Soc. 116 (1994) 3647; (b) B.L. Edelbach, R.J. Lachicotte, W.D. Jones, J. Am. Chem. Soc. 120 (1998) 2843; (c) T. Mitsudo, S.W. Zhang, Y. Watanabe, J. Chem. Soc. Chem. Commun. (1994) 435. W.D. Jones, J.A. Maguire, Organometallics 6 (1987) 1301. B. Machura, R. Kruszyński, M. Jaworska, J. Kłak, J. Mroziński, Polyhedron 25 (2006) 2537. (a) L. Fuks, E. Gniazdowska, P. Kozmiski, Polyhedron 29 (2010) 634; (b) S.M. Harben, P.D. Smith, R.L. Beddoes, D. Collison, C.D. Garner, J. Chem. Soc. Dalton Trans. (1997) 2777. (a) S. Jurisson, L. Francesconi, K.E. Linder, E. Treher, M.F. Malley, J.Z. Gougoutas, A.D. Nunn, Inorg. Chem. 30 (1991) 1820; (b) J. Rall, F. Weingart, D.M. Ho, M.J. Heeg, F. Tisato, E. Deutsch, Inorg. Chem. 33 (1994) 3442; (c) B. Machura, J. Mroziński, R. Kruszyński, J. Kusz, Polyhedron 27 (2008) 3013; (d) N.D. Paul, S. Samanta, T.K. Mondal, S. Goswami, Inorg. Chem. 50 (2011) 7886. (a) F.A. Cotton, L.D. Gage, C.E. Rice, Inorg. Chem. 18 (1979) 1138; (b) B. Machura, J. Mroziński, R. Kruszyński, J. Kusz, Polyhedron 27 (2008) 3013. (a) J. Chatt, G.J. Leigh, D.M.P. Mingos, E.W. Randall, D. Shaw, Chem. Commun. (1968) 419; (b) E.W. Randall, D. Shaw, J. Chem. Soc. A (1969) 2867. (a) B. Machura, M. Wolff, R. Kruszyński, J. Mroziński, J. Kusz, Polyhedron 28 (2009) 2377; (b) B. Machura, R. Kruszyński, M. Jaworska, J. Mol. Struct. 740 (2005) 107. (a) W.P. Griffith, T.D. Wickins, J. Chem. Soc. A (1967) 675; (b) A. Guest, C.J.L. Lock, Can. J. Chem. 49 (1971) 603; (c) B. von Malottki, W. Preetz, Z. Anorg. Allg. Chem. 626 (2000) 1681; (d) B. Jeżowska-Trzebiatowska, J. Hanuza, M. Bałuka, Spectrochim. Acta 27A (1971) 1753. (a) A. Valor, E. Reguera, E. Torres-Garcia, S. Mendoza, F. Sanchez-Sinencio, Thermochim. Acta 389 (2002) 133; (b) M.C. Rusjan, E.E. Sileo, F.D. Cukiernik, Solid State Ionics 124 (1999) 143.
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Cleavage of a C\C bond during a solvothermal process leading to a mononuclear rhenium(III) product Andrzej Kochel a,⁎, Małgorzata Hołyńska b,⁎, Kamil Twaróg a a b
University of Wrocław, Faculty of Chemistry, F. Joliot-Curie 14, 50‐383 Wrocław, Poland Fachbereich Chemie, Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35043 Marburg, Germany
a r t i c l e
i n f o
Article history: Received 9 May 2012 Accepted 23 July 2012 Available online 29 July 2012 Keywords: Rhenium(III) Solvothermal conditions Cleavage of C\C bond
a b s t r a c t A new system is reported, where solvothermal conditions lead to a cleavage of a C\C bond in 2,2′-bipyridine-3,3′,6,6′-tetracarboxylic acid, that might be catalyzed by the starting rhenium salt, ammonium hexachloridorhenate(IV). The resulting product (1) is a rhenium(III) complex, including the applied ligand and its decomposition product in the Re3+ ion coordination sphere. 1 is characterized by X-ray diffraction, magnetic and spectroscopic, as well as TGA property measurements. © 2012 Elsevier B.V. All rights reserved.
Solvothermal synthesis in rhenium chemistry is relatively seldom represented [1]. The conditions applied during such syntheses may favor unexpected side-reactions, including catalytic processes [2]. Bond activation in solvothermal processes might lead to formation of new organic ligands, also involving C\C bond formation [3a–c]. Activating role of metal ions in such syntheses has been well investigated in the case of copper(II) ions [3d–f]. The title compound (1) was synthesized as a continuation of our project on solvothermal syntheses in rhenium coordination chemistry with the use of amine ligands, leading to compounds with unusual molecular topologies/potential radiopharmaceuticals [3g–h]. 1 is a mixed salt containing complex (2,2′-bipyridine-6, 6′-(dicarboxylic acid)-3,3′-dicarboxylato)(pyridine-2,5-dicarboxylato-N, O)chloridorhenium(III) molecules, sodium cations and chloride anions obtained in a solvothermal reaction between 2,2′-bipyridine-3,3′,6, 6′-tetracarboxylic acid and ammonium hexachloridorhenate(IV) under basic conditions. The Re3+ ion coordination sphere includes both the applied ligand, and its degradation product. Apparently a potentially catalytic process leading to a cleavage of the C\C bond joining two pyridyl rings in the 2,2′-bipyridine-3,3′,6,6′-tetracarboxylic acid takes place, involving the release of oxygen gas as a by-product. This is confirmed by control of oxygen concentration by means of an oxygen sensor (see ESI). The 2,2′-bipyridine-3,3′,6,6′-tetracarboxylate ligand (H2L1) was first introduced by Dawid et al. [4] as part of studies on design and synthesis of nitrogen/oxygen-donor ligands combined with multicarboxylic acids. Binuclear iron(II) and cobalt(II) compounds were also reported as the so far sole examples of metal complexes with ligand L1. On the other ⁎ Corresponding authors. E-mail addresses: [email protected] (A. Kochel), [email protected] (M. Hołyńska). 1387-7003/$ – see front matter © 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.inoche.2012.07.042
hand, a C\C bond cleavage catalyzed by transition metal complexes has been reported for many cases, including mainly Rh, Pd, Pt, as well as Fe, Co, Ru and Zr [5], whereas rhenium-catalyzed processes are less frequently reported [6]. The experimental procedure leading to 1 may be summarized as shown in Scheme 1. A potentially catalytic C\C bond cleavage within the ligand L 1 takes place. A rhenium(III) product is formed by reduction of the hexachloridorhenate(IV) starting compound and is isolated as crystalline material at 56% yield. The oxygen side-product is identified with the aid of an oxygen sensor (see Experimental). However, no detailed conclusions on the potentially catalytic cycles can be drawn from this study. When the analogous synthesis conditions are applied without the use of rhenium(III) starting material, no degradation of the starting carboxylic acid is observed. Coordination environment of the Re3+ ion includes one tetradentate 2,2′-bipyridine-6,6′-(dicarboxylic acid)-3,3′-dicarboxylato ligand (L1), one bidentate pyridine-2,5-dicarboxylato ligand (L2) and one chlorido ligand (Fig. 1). The Re\Clterminal bond length is of 2.344(2) Å (Table S2), which is similar as in related compounds [7]. Pyridine N12 atom of the ligand L2 is coordinated trans to the terminal chlorido ligand. L2 is also coordinated to the Re3+ ion by carboxyl O22 atom. To the best of our knowledge coordination of a non-deprotonated carboxylic group to Re3+ ion has never been reported, on the other hand, it is known for rhenium complexes at both lower and higher oxidation states [8]. The remaining four coordination places are filled with two pyridine N atoms (N1, N11) and two carboxylate O atoms (O1, O11) of the ligand L1. Thus the central Re3+ ion has coordination number 7, already reported for mononuclear rhenium(III) complexes [9]. The Re\Ocarboxyl bond lengths are at 2.022(3)–2.064(3) Å range and the Re\Npyridyl bond lengths are
48
A. Kochel et al. / Inorganic Chemistry Communications 24 (2012) 47–49
Scheme 1. General scheme for the preparation of 1.
from 2.080(3) to 2.111(4) Å, which is typical among related rhenium(III) complexes [10]. Within the ligand L1 the planes of two pyridyl rings are twisted with respect to each other by 20.6(2)° with N atoms in a cis arrangement, whereas for the free ligand the corresponding angle is of 49.87(4)° and the pyridyl N atoms are trans to each other [4]. The O11and O1-containing carboxylate group planes are twisted with respect to their parent pyridyl rings by 19.8(4) and 25.1(4)°, respectively. The corresponding twist angles for the carboxyl groups not participating in coordination to the central metal ion are 35.8(4) and 31.6(5)° for the O31- and O3-containing group, respectively. In the ligand L2 the non-coordinated O32-carboxyl group is almost coplanar with the N12-pyridyl ring, whereas the O22-coordinated carboxyl group plane is twisted with respect to the same pyridyl ring by 12.8(8)°. 1 contains also Na+ and Cl− ions. The symmetry-independent Na1 cation includes in coordination sphere two water molecules and four carboxyl/carboxylate O atoms from three independent complex molecules. Each symmetry-independent Cl− ion is involved in three O\H…Cl hydrogen bonds with one water molecule of solvation and L 1/L 2 carboxyl groups from two independent complex molecules acting as donors. Na\O coordination bonds stabilize the formation of layers in the crystal structure (Fig. 2, Table S2), governing the crystal structure, in which no significant stacking interactions between aromatic rings could
Fig. 2. One of the layers stabilized by Na\O bonds in 1, projected along [010]. C/H atoms are shown as sticks, the remaining atoms are plotted as spheres of arbitrary radii.
be found. The layers are interconnected by O\H…O and O\H…Cl type hydrogen bonds (Table S3). The new material was characterized in terms of magnetic and spectroscopic properties, as well as its thermal decomposition. Magnetic properties of 1 were investigated in the temperature range from 1.8 to 300 K under the applied magnetic field of 1 T (see Fig. 3 for χm and χmT vs. T plots). 1 shows an overall paramagnetic behavior. Spin-only magnetic momentum at room temperature is of 1.88 B.M., which corresponds to the χmT value of 0.446 cm3mol−1 K. Magnetic momentum of 1 is weakly temperature-dependent, dropping to 1.45 B.M. at 1.8 K. These values are characteristic for monomeric low-spin Re3+ ions (d 4) in Oh ligand field, which corresponds to a 3T1g ground state [11]. Electronic spectra collected for aqueous solutions of 1 are comparable to those reported for related rhenium(III) complexes and apparently dominated by MLCT bands [12] (see ESI).
Fig. 1. Molecular structure of complex 1 with atom labeling scheme. Thermal displacement ellipsoids are plotted at 30% probability level. H atoms are shown as spheres of arbitrary radii.
A. Kochel et al. / Inorganic Chemistry Communications 24 (2012) 47–49
49
0.5
0.16
0.45
0.14
0.4
0.2
-1
0.25
0.1 0.08
3
0.3
XmT [ cm mol K]
X m [cm 3 mol -1]
0.12 0.35
0.06
0.15 0.04 0.1 0.02
0.05 0 0
50
100
150
200
250
0 300
T [K] Fig. 3. χmT (dots) and χm vs. T (triangles) plots illustrating the magnetic properties of 1.
IR spectrum recorded for 1 is dominated by bands arising from the organic ligand. At 2500–3600 cm−1 broad bands assignable to νOH are observed [4]. Broad band at 1627 cm−1 can be assigned to νas(COO), whereas the bands at 1378, 1409 and 1457 cm−1 should arise from νs(COO), combined for coordinated/uncoordinated and protonated/ deprotonated carboxyl groups [4]. Weak band at 316 cm−1 on the FIR spectrum may confirm the presence of a Re\Cl bond [13]. A very strong band at 149 cm−1 with a broad shoulder reaching 300 cm−1 and weaker bands extending to lower wavenumbers may be a result of a combination of νas(Re\Cl) and δ(ClReO), δ(NReO), δ(NReN) [13]. 1, as revealed by its TGA diagram (Fig. S2), undergoes a stepwise decomposition on heating under nitrogen atmosphere. First step apparently involves release of water of solvation, combined with partial decomposition of the organic part, possibly decarboxylation of the organic ligands [14]. At about 235 °C the sample undergoes melting with further decomposition in at least two steps. Mass of the residue after the whole decomposition process may correspond to the total Na + Cl + Re content of 1. To sum up, a new system has been reported, where solvothermal conditions lead to the cleavage of the C\C bond in 2,2′-bipyridine3,3′,6,6′-tetracarboxylic acid, that might be catalyzed by the starting rhenium salt. The resulting product is a rhenium(III) complex, including the applied ligand and its decomposition product in the Re3+ ion coordination sphere, providing a new insight into the chemistry of solvothermal processes involving rhenium compounds.
(b) (c) (d) [2] (a) (b) [3] (a)
[4] [5]
[6] [7] [8]
[9]
[10]
Acknowledgments
[11]
Helpful discussions by Dr. Jarosław Sobczak and Dr. Jacek Wojaczyński are gratefully acknowledged.
[12]
[13]
Appendix A. Supplementary data Supplementary data to this article can be found online at http:// dx.doi.org/10.1016/j.inoche.2012.07.042. References [1] (a) M.N. Sokolov, N.E. Fedorova, N.V. Pervukhina, E.V. Peresypkina, A.V. Virovets, R. Petov, V.E. Fedorov, D. Fenske, Izv.Akad.Nauk SSSR,Ser.Khim.(Russ), Russ. Chem. Bull. (2006) 52;
[14]
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