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N-substituted monodentate alcohols as ligands modifying structure, properties and thermal stability of Mo(IV) complexes
Journal of Molecular Structure 1081 (2015) 6–13
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Journal of Molecular Structure journal homepage: www.elsevier.com/locate/molstruc
N-substituted monodentate alcohols as ligands modifying structure, properties and thermal stability of Mo(IV) complexes Anna Jurowska a,⇑, Janusz Szklarzewicz a,⇑, Maciej Hodorowicz a, Monika Tomecka a, Janusz Lipkowski b, Wojciech Nitek a a b
Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Kraków, Poland Institute of Physical Chemistry of PAN, Kasprzaka 44, 01-224 Warsaw, Poland
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Three new Mo(IV) complexes with
monodentate ligands were synthesised. All complexes have been characterized by single crystal X-ray crystallography. Analysis, IR, UV–Vis, CV and DTG are presented and discussed.
a r t i c l e
i n f o
Article history: Received 12 September 2014 Received in revised form 2 October 2014 Accepted 2 October 2014 Available online 13 October 2014 Keywords: Molybdenum Aminoalcohols X-ray crystal structure Thermogravimetry Electronic spectra
a b s t r a c t The reaction of N-substituted alcohols (2-aminoethanol, 3-amino-1-propanol and 2-hydroxyethylhydrazine) with K3Na[Mo(CN)4O2]6H2O in water–ethanol solution results in isolation of three new complexes of formulae: (PPh4)2[Mo(CN)4O(amet)]3H2O (1), (amet = 2-aminoethanol), (PPh4)2[Mo(CN)4 O(ampro)]3H2O (2) (ampro = 3-amino-1-propanol) and (PPh4)2[Mo(CN)4O(ethyd)]3H2O (3) (ethyd = 2-hydroxyethylhydrazine). The isolated salts were characterized by elemental analysis, single crystal X-ray structure measurements, IR and UV–Vis spectroscopy and cyclic voltammetry. The complexes crystalize in triclinic space group with distorted octahedral geometry of the anion. The obtained salts belongs to a very rare group of complexes with monodentate terminal N-donating alcohols. The thermal stability is described for all complexes and compared with crystal structure parameters. Ó 2014 Elsevier B.V. All rights reserved.
Introduction They are very limited data with regard to the cyanido complexes of Mo(IV) with monodentate ligands of the ion formula [Mo(CN)4O(L)]n (where n = 2–4) [1]. The main type of L ligands are inorganic anions as CN , N3 , F , OH , O2 , H2O, HCN, NH3, little is known about organic ligands. The first isolated, in very drastic ⇑ Corresponding authors. Tel.: +48 12 6632223; fax: +48 12 6340515. E-mail addresses: [email protected] (A. Jurowska), szklarze@chemia. uj.edu.pl (J. Szklarzewicz). http://dx.doi.org/10.1016/j.molstruc.2014.10.005 0022-2860/Ó 2014 Elsevier B.V. All rights reserved.
conditions, were with L = aliphatic diamines (as etylenediamine, propylenediamine, and other ligands) bonded in monodentate way [2]. The complexes with 2-pyridinecarboxaldehyde, pyridine and pyrazine in water–ethanol solutions were also synthesized [3–5]. The main problem connected with such synthesis is a very weak bonding of organic ligands, being in trans position to a very short Mo@O bond. Moreover, the complexes have to be isolated as their tetraphenylphosphonium salts as the alkali metal salts are too basic and decomposition of these complexes is observed. On the other hand, tetraphenylphosphonium salts were found to be very reactive both in solution and in solid state, for example
A. Jurowska et al. / Journal of Molecular Structure 1081 (2015) 6–13
they react with molecular oxygen with formation of peroxo complexes with the anion formula [Mo(CN)4O(O2)]2 , molybdenum is oxidized to +6 formal oxidation state [6]. In present paper we decided to extend our knowledge on complexes with ligands possessing amino and hydroxyl group. As ligands we used 2-aminoethanol, 3-amino-1-propanol and 2hydroxyethylhydrazine. The structure of compounds with 2hydroxyethylhydrazine have not yet been described up to our knowledge. The 2-aminoethanol and 3-amino-1-propanol can be coordinated to a metal center both as N- or O-donating ligands. As monodentate ligands they can be coordinated by nitrogen [7] or oxygen atom [8] even for the same metal center, in summary 43 structures of such a coordination mode were described [9]. For metal complexes 19 are with MeAN, while only 10 with MeAO as donor atom. Much more often 2-aminoethanol and 3-amino-1-propanol acts as bidentate ligand [10] or even tridentate [11]. In this paper we obtained complexes with only monodentate N-donating ligands. This gave us unique possibility to study the intermolecular interactions and to compare the physicochemical properties of complexes with different R substituents in L ligand of general formula H2NARAOH. The thermal stability is drown from the intermolecular interactions present in solid state. These data are of special interest as all complexes belongs to a very rare class in which the formula is almost identical, salts are isostructural, poses the same number of hydration waters, similar hydrogen bonds net and only difference is that amino alcohols ligands differs by NH2AOH distance (from CAC, CACAC to NHACAC separation). This allows us for a very precise correlation between structure and thermal stability. Experimental Materials and methods K3Na[Mo(CN)4O2]6H2O was synthesized according to published methods [1d]. All other chemicals were of analytical grade (Aldrich) and were used as supplied. Microanalysis of carbon, hydrogen and nitrogen were performed using Elementar Vario MICRO Cube elemental analyzer. Thermogravimetric analysis were performed on a TGA/SDTA 851e Mettler Toledo apparatus. The studied complexes were placed in open alumina crucibles (150 ll) and were heated from 25 to 650 °C with constant heating rate 10 °C/min under Ar flow (80 ml/min). The temperature was measured by a Pt–Pt/Rh thermocouple with the accuracy of ±0.5 °C. Solid samples for IR spectroscopy were recorded on a Nicolet iS5 FT-IR spectrophotometer. The electronic absorption spectra were recorded with Shimadzu UV-3600 UV–VIS–NIR spectrophotometer equipped with a CPS-240 temperature controller. Diffuse reflectance spectra were measured in BaSO4 pellets with BaSO4 as a reference on Shimadzu 2101PC equipped with an ISR-260 integrating sphere attachment. Cyclic voltammetry measurements were carried out in MeCN (acetonitrile) with [Bu4N]PF6 (0.1 M) as the supporting electrolyte, using Pt working and counter and Ag/AgCl reference electrodes on an AUTOLAB/PGSTAT 128 N Potentiostat/Galvanostat. E1/2 values were calculated from the average anodic and cathodic peak potentials, E1/2 = 0.5 (Ea + Ec). The redox potentials were calibrated versus ferrocene (0.440 V versus SHE), which was used as an internal potential standard for measurements in organic solvents to avoid the influence of a liquid junction potential; the final values are reported versus the standard hydrogen electrode (SHE). Synthesis of (PPh4)2[Mo(CN)4O(L)]3H2O, L = amet, ampro and ethyd (1–3) The complexes (PPh4)2[Mo(CN)4O(amet)]3H2O (1), (PPh4)2[Mo(CN)4O(ampro)]3H2O (2) and (PPh4)2[Mo(CN)4
7
O(ethyd)]3H2O (3) were synthesized in water–ethanol solutions. All three ligands: 2-aminoethanol, 3-amino-1-propanol and 2-hydroxyethylhydrazine (10 mmol) were dissolved in 10 ml of ethanol and heated to 40 °C for several minutes. The solution of K3Na[Mo(CN)4O2]6H2O (1 mmol) in 20 ml of water was added to these three ligands separately. Then solid PPh4Br (1 mmol) was added and the obtained blue crystals were filtered off, washed with the water and dried in air at room temperature. The yields are: 58%, 42% and 67% for 1, 2 and 3 respectively. The Anal. Calcd. for C54H53MoN5O5P2 (1): C, 64.29; H, 5.20; N, 6.94%. Found: C, 64.55; H, 5.25; N, 6.91%, Anal. Calcd. for C55H55MoN5O5P2 (2): C, 64.58; H, 5.32; N, 6.85%. Found: C, 64.86; H, 5.22; N, 6.78% and Anal. Calcd. for C54H54MoN6O5P2 (3): C, 63.28; H, 5.31; N, 8.20%. Found: C, 63.25; H, 5.39; N, 8.36%. Crystallographic data collection and structure refinement Diffraction data for single crystal of (PPh4)2[Mo(CN)4O(amet)]3H2O (1), (PPh4)2[Mo(CN)4O(ampro)]3H2O (2) and (PPh4)2[Mo(CN)4O(ethyd)]3H2O (3) were collected at 140, 100 and 293 K for 1, 2 and 3 respectively on the Oxford Diffraction SuperNova four circle diffractometer, using the Cu (1.54180 Å) for 1 and Mo (0.71069 Å) for 2 and 3 Ka radiation source and graphite monochromator. Cell refinement and data reduction was performed using firmware [12]. Positions of all of non-hydrogen atoms were determined by direct methods using SIR-97 [13]. All non-hydrogen atoms were refined anisotropically using weighted full-matrix least-squares on F2. Refinement and further calculations were carried out using SHELXL-97 [14]. Moreover, several restraints, such as EDAP, SIMU, DELU and ISOR, were applied to deal with the disordered atoms or groups. All hydrogen atoms joined to carbon atoms were positioned with an idealized geometry and refined using a riding model [with Uiso(H) fixed at 1.5 Ueq of C for methyl groups and 1.2 Ueq of C for other] whereas hydrogen atoms of AOH, ANH2 groups were included from the difference maps and were refined with isotropic thermal parameters. In the structure 1 at the oxygen atom O(13) (water molecule) is unable to find the hydrogen atoms from difference Fourier map. The 2aminoethanol group (in 1) coordinated to molybdenum atom is disordered and all atoms N5, C6, C7 and O2 were refined in two complementary positions. Additionally the bond lengths N5A– O2A and N5B–O2B were restrained during refinement to preserve proper geometry. Results and discussion Description of crystal structures Compounds 1 and 2 are isostructural with 3. Single-crystal Xray study reveals that the asymmetric part of the unit cells of the complexes 1, 2 and 3 have similar stoichiometry: [Mo(CN)4O(L)]2 anion, L = 2-aminoethanol (1), 3-amino-1-propanol (2), 2-hydroxyethylhydrazine (3), two PPh+4 cations and three water molecules of solvation (Fig. 1a–c). The crystallographic data and detailed information on the structure solution and refinement for 1, 2 and 3 are given in Table 1 and Table S1 in Supporting information. Although the measurement was held in 140 K, the ethanolamine ligand (1), shows a dynamic disorder (labeled as N5A–O2A and N5B–O2B). One of the three water molecules for structures 2 and 3, H2O(16), shows static disorder and consequently partial occupancy (site occupancy factor 0.63 and 0.75 for 2 and 3 respectively). In all three structures the [Mo(CN)4O]2 moiety adopts the same conformation in that the cyanido ligands are arranged in an equatorial square plane (the coordinated Mo(1) atom is located
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Fig. 1. Single-crystal X-ray structure of 1, 2 and 3 showing the atom labeling scheme and 30% displacement ellipsoids.
Table 1 Crystal data and structure refinement parameters for 1, 2 and 3.
Empirical formula Formula weight Crystal size (mm) Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) h k l V (Å3) Z T (K) Dx (Mg/m3) Reflections collected Independent reflections Final R indices [I > 2sigma(I)] R indices (all data) Goodness-of-fit on F2
1
2
3
C54H51MoN5O5P2 1007.88 0.42 0.26 0.07 Triclinic P1
C55H54.25 Mo N5O4.63 P2 1017.18 0.200 0.200 0.200 Triclinic P1
C54H53.50MoN6O4.75P2 1024.40 0.230 0.140 0.080 Triclinic P1
13.377(5) 13.821(5) 16.326(5) 109.018(5) 90.799(5) 118.683(5) 16 to 16 16 to 16 19 to 20 2450.10(15) 2 140 1.366 36,548 18,986 [R(int) = 0.0217] R1 = 0.0312, wR2 = 0.0791
13.422(3) 13.744(4) 16.505(4) 70.286(2) 89.707(2) 61.640(3) 17 to 18 18 to 18 22 to 22 2477.45(13) 2 100 1.364 42,304 9,391 [R(int) = 0.0328] R1 = 0.0257, wR2 = 0.0647
13.5844(5) 13.9093(5) 16.6740(6) 110.019(3) 90.163(3) 118.842(4) 18 to 18 18 to 17 22 to 22 2538.40(19) 2 293 1.340 37,060 11,876 [R(int) = 0.0432] R1 = 0.0490, wR2 = 0.1038
R1 = 0.0359, wR2 = 0.0824 1.019
R1 = 0.0286, wR2 = 0.0666 1.024
R1 = 0.0876, wR2 = 0.1344 1.098
at 0.445(1) Å for 1, 0.586(1) Å for 2 and 0.449(2) Å for 3 over the cyanido N4 plane, Fig. 1a) with an average MoAC distances 2.164 Å for 1, 2.163 Å for 2 and 2.159 Å for 3. These distances are typical for complexes with monodentate N-donating ligands [1]. An average OAMoAC bond angles are 100,15°, 100,35° and 100,23° for 1, 2 and 3 respectively and are very similar to these found in other complexes of Mo(IV) with monodentate N-donating ligands e.g. the average bond angles are: 100,78° for NH3 ligand [15], 101,63° for ethylenediamine (en) ligand [2], 100,68° for 2pyrazinecarbonitrile (pcn) ligand [16] and 101,20° for HCN ligand [1b]. The oxo ligand in axial position (the apex of a square pyramid) is significantly closer to molybdenum(IV) ion than four cyanido groups and it forms short Mo@O bond (1.676(2) Å for 1, 1.681(1) Å for 2 and 1.658(2) Å for 3). The interatomic bond distances of Mo@O are comparable with other characterized cyanidooxocomplexes of molybdenum(IV) with monodentate ligands. For (PPh4)2[Mo(CN)4O(NH3)]2H2O this distance is 1.661 Å [15], for complex with en 1.666 Å [2], with pyrazine (pz) 1.662 Å [4], with pcn 1.653 Å [16] and with HCN ligand 1.655 Å [1b]. All these bonds are relatively short and can be treated as a triple bond (Mo„O 1.65 Å) according to the Cotton classification [17].
Additionally in position trans to the oxo ligand, N-substituted alcohol (L) molecule is located, L = 2-aminoethanol for 1, 3amino-1-propanol for 2 and 2-hydroxyethylhydrazine for 3. These molecules form relatively long Mo–N5 bond (2.426(5), 2.412(1) and 2.401(3) Å for 1, 2 and 3 respectively) and they are similar to bond length observed in complex with NH3 and HCN ligands (2.422 and 2.435 Å respectively) [15,1b]. Considerably longer analogous MoAN bond has been observed in complexes with en ligand (2.491 Å) [2], with pz ligand (2.569 Å) [4] and with pcn ligand (2.538 Å) [16]. These differences in lengths of coordination bond cause the distortion of coordination octahedron (Table S1 in Supporting information). In complexes with another than molybdenum metal center (e.g. Cu and Fe) and with 2-aminoethanol or 3-amino-1-propanol as N-donating ligand, these distances are much shorter, e.g. CuAN is 2.038 Å (for complex with 2-aminoethanol) [18] and FeAN is 2.021 Å (for complex with 3-amino-1-propanol) [19]. Only for Pb complex with 2-aminoethanol the PbAN distance is also long (2.554 or 2.564 Å) due to radius of Pb ion [20]. Analysis of the crystal structure of 1, 2 and 3 at the supramolecular level reveals that the complex molecules are held together by two T-shape hydrogen CAH p and OAH p bondings (Fig. 2) and
A. Jurowska et al. / Journal of Molecular Structure 1081 (2015) 6–13
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Fig. 2. The CAH p bonds in 2.
Fig. 3. The hydrogen bonds in 2. The cations are omitted for clarity.
several hydrogen interactions (Fig. 3), which are summarized in Tables S2–S5 in Supporting information. The XAH p contact can be classified by type IV, according to Malone [21]. The crystal contains inorganic coordination chains running along the c direction, in which the structural unit containing two neighboring Mo(IV) ions linked (see Fig. 3). The lattice water molecules participates in many hydrogen bonds of OAH O and OAH N type linking belonging to the structural units of adjacent ribbons (Fig. 3). The water molecules at (x, y, z) participate in O(14)AH(14A) O(15)[x + 1,y,z] and O(15)AH(15B) O(14)[ x,+1y, z+2] hydrogen bonds, forming small R44(8) rings [22]. All these interactions are responsible for self-assembly of the complexes molecules and stabilization of 3D structures. The shortest intermolecular Mo Mo distances are 8.907(2) Å, 9.555(2) Å, 9.474(4) Å for 1, 2 and 3 respectively.
IR spectra In the infrared spectra the mMo@O band positions in 1, 2 and 3 (964, 960 and 964 cm 1, respectively) are in the range typical for analogous [Mo(CN)4O(L)]n complexes, where L can be N-donor ligands [1] (see Fig. 4). In all three complexes the bands located at 2091, 2103, 2115 cm 1 for 1, at 2088, 2104, 2119 cm 1 for 2 and at 2091, 2104, 2119 cm 1 for 3 are observed and can be assigned to the vibration connected with cyanido ligands. The similar situation is observed for the Cs2Na[Mo(CN)5O] and (PPh4)2 [Mo(CN)4O(py)]2H2O (py = pyridine) complexes, where these bands are located at 2064, 2108, 2122 cm 1 and at 2089, 2098, 2111 cm 1 respectively [1a,4]. In literature it was found, that in complexes with monodentate ligands except three bands, one, two or even four cyanido bands can be observed. For
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Fig. 4. The ATR-FTIR spectra of 1 (black line), 2 (red line) and 3 (blue line). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 7. Cyclic voltammogram of 1 in MeCN and 0.1 M Bu4NPF6 as electrolyte. In the upper left corner voltammograms recorded at different scan speeds are shown.
Table 2 Cyclic voltammetry data.
Fig. 5. UV–Vis spectra of 1 in EtOH and DMSO (dotted line).
Fig. 6. UV–Vis reflectance spectra of 1 (black line), 2 (red line) and 3 (blue line) in BaSO4 after Kubelka–Munk transformation. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
V (mV/s)
Ea1 (V)
Ea2 (V)
Ek1 (V)
20 50 100 200 500 1000
0.260 0.262 0.272 0.277 0.314 0.320
0.372 0.376 0.391 0.397 – –
– – – – 0.152 0.153
Ek2 (V) 0.023 0.018 0.002 0.012 0.024 0.038
DV (Ea1
Ek1) (V)
– – – – 0.162 0.167
(PPh4)2[Mo(CN)4O(pcn)]2H2O (pcn = 2-pyrazinecarbonitrile) only one band at 2091 cm 1 appeared [16], for (PPh4)2[Mo(CN)4O(NH3)] two bands at 2084 and 2110 cm 1 are observed [15] and for (PPh4)2[Mo(CN)4O(pz)]3H2O (pz = pyrazine) four bands are located at 2085, 2088, 2094 and 2103 cm 1 [5]. The number of bands in the region characteristic for vibration of cyanido ligands depends on an anion symmetry and specific position of CN versus L ligands. Salts 1, 2 and 3 are isostructural and cyanido ligands location is almost similar, thus all three complexes have the same number of the cyanido bands. The band at 3657 cm 1 is connected with the stretching of the hydroxyl group of monodentate ligands. In the other regions, at 1100 and 997 cm 1 the bands typical for PPh4 cation are observed for all three compounds.
Fig. 8. TG and DTG curves for complex 1.
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Cyclic voltammetry measurements The recorded cyclic voltammogram for 1 is presented on Fig. 7 while the data are presented in Table 2. Two oxidation peaks at 0.272 and 0.391 V and one reduction peak at 0.002 V are observed (at 100 mV/s). The complexes with monodentate ligands are unstable in solutions, as it was seen on Fig. 7, with L ligand exchange into solvent molecule, thus cyclic voltammograms of all salts 1, 2 and 3 are similar. In general two oxidation peaks are observed: the peak at lower potential can be assigned to [Mo(CN)4 O(L)] /2 (L = solvent) and the second peak is connected with redox system of the decomposition products of oxidized [Mo(CN)4O(L)]2 molecule. Detailed study of the process, at various scan speed (Fig. 7) shows, that the peak position is only merely dependent on the scan speed and at 500 mV/s the reduction peak starts to be observed. Such behavior is typical for reversible redox process, in which, after oxidation, the compound undergoes chemical reactions.
Fig. 9. TG and DTG curves for complex 2.
Thermogravimetry
Fig. 10. TG and DTG curves for complex 3.
UV–Vis spectra The UV–Vis measurements shows that the complexes release L ligand in solutions with formation of [Mo(CN)4O(solv)]2 ion (Fig. 5). Thus only the reflectance spectra can give proper energy of d–d transitions observed in visible part of the spectra (see Fig. 6). The very close similarity of ligands L in 1, 2 and 3 is reflected in d–d band positions, which are 638, 626 and 623 nm for 1, 2 and 3 respectively.
The TG and DTG curves for the hydrated complexes 1–3 are shown in Figs. 8-10 respectively. The numerical data are collected in Table 3. For all salts similar decomposition pattern is observed. In the first step water of hydration is released, then organic ligand (for salts 1 and 2 this decomposition is overlapped with partial cation release) and finally the cations. At higher temperatures than 500 °C also cyanido ligands are released. This can be especially well seen for salt 1, where TG up to 1000 °C was measured (the measurement above 650 °C were performed only for 1 as measurements above 650 °C are dangerous for apparatus as MoO3 can start to sublimate). Moreover under Ar atmosphere it is difficult to get well defined product of molybdenum complexes decomposition (in most cases mixture of MoO3 and molybdenum carbides is observed). The observed DTG peaks indicate that the lowest decomposition temperature is for salt 2, then for 3 and 1. The detailed study of the hydrogen bond distances indicate that this order is reflected in the bond lengths between cyanide nitrogen and hydroxyl oxygen (2.752, 2.746 and 2.739 Å respectively for 2, 3 and 1) and is not reflected in any other order of hydrogen bond distances involving water molecules. As shown in Fig. 11, this bond keeps two anions together. It seems, that order of DTG maxima suggests that the dehydration of salts 1–3 starts from NAO bond breaking, which breaks anion – anion interaction. Above and below the presented in
Table 3 Thermal data for the decomposition of complexes 1–3. Complex
Temp. range (°C)
DTG peak (°C)
Obs. wt. loss Dm/m (%)
Calc. wt. loss Dm/m (%)
Evolution of
1
25–138 138–208 208–313 313–583 583–733 733–1000 5–171 171–306 306–383 383–608 25–119 119–147 147–205 205–319 319–419 419–562 562–646
97.7 203.0 293.0 326.0 669.0 – 89.2 283.3 318.3 401.2 92.2 131.7 195.8 296.2 334.2 440.5 –
4.81 8.66 36.46 76.34 82.27 84.14 6.54 36.59 70.68 81.60 3.80 6.14 10.42 34.08 70.08 75.57 77.77
5.36 8.38 36.30 78.68 81.36 84.04 5.31 36.68 70.01 81.99 3.51 5.27 12.69 35.85 70.27 76.89 78.88
3H2O 0.5 amet 0.5 amet, 0.74 PPh4 1.26 PPh4 HCN HCN 3H2O ampro, 0.72 PPh4 PPh4 0.28 PPh4, HCN 2H2O H2O ethyd 0.7 PPh4 1.04 PPh4 0.2 PPh4 0.06 PPh4
2
3
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Fig. 11. The hydrogen bonds in 1, 2 and 3.
Fig. 11 member ring (MoACNAligand’AMo’ACN’AligandAMo, where ligand denote amet, ampro or ethyd) the perpendicular phenolic rings of PPh+4 cations are presented. After breaking the hydrogen bonds, they can separate anions and in effect causes the collapse of the structure. The water of hydration now can be easily removed. There is no correlation between MoAN (from organic ligand) bond length and DTG maximum position for organic ligand release. The DTG maxima are at 203, 283 and 195 °C, while the MoAN bond lengths are 2.426(1), 2.412(2) and 2.401(3) Å for 1, 2 and 3 respectively. This is expected feature, as hydrogen bonds affect the MoAN distance. When hydroxyl group of ligand becomes ‘‘free’’ the MoAN distance change and as a result there is no direct correlation between DTG maxima position and structural data. After alcohol release, the Mo(IV) becomes unsaturated and decomposition of complex accompanied by redox processes starts. This is responsible for partial cation release, and at higher temperatures for cyanido ligands (probably in form of HCN or (CN)2) release. Conclusions The aminoalcohols are often used and they can serve as selfadopting to metal center multidentate ligands. In the most cases, they form bonds with typical metal-nitrogen distance, similar to that in other amines as ligands. In complexes 1–3 the MoAN distance is in contrary very long, nevertheless for these N-substituted alcohols influence on complex properties still can be well recognized. All studied salts 1–3 are isostructural, have the same numbers of cations and water of hydration, have the same metal arrangement. However, even for very geometrically similar ligands in 2 and 3 specific ligand effect is observed. For example the MoAN bond distance changes in order 1 > 2 > 3, Mo@O bond (trans to MoAN) changes in order 2 > 1 > 3, while the mMo@O changes in order 1 = 3 > 2. This, as found by structural study, is not an effect of steric hindrances, but rather should be interpreted as specific electronic effect. This is especially well seen for hydrazine analogue in 3, where change of carbon atom into nitrogen one results in change of physicochemical properties. The most striking is the position of the d–d bands in electronic spectra, supporting the specific electronic ligand effect. The specific ligand effect is also strongly reflected in thermogravimetric measurements. Although the TG curves look different for all salts, the decomposition patter is very similar. The DTG maxima positions for 1–3 indicate that the dehydration process starts from cyanide nitrogen–oxygen from hydroxyl group hydrogen bond breaking. This process breaks anion–anion interaction what yields the structure collapse and as a result water of hydration can be removed. Acknowledgements The research was carried out partially with the equipment purchased thanks to the financial support of the European Regional Development Fund in the framework of the Polish Innovation Economy Operational Program (Contract No. POIG.02.01.00-12023/08).
This work was made by the scholarship support of the first author by the Krakow Marian Smoluchowski Consortium ‘‘Matter–Energy–Future’’ (KNOW grant). Appendix A. Supplementary material CCDC 1002391, 1002392 and 1002393 contains the supplementary crystallographic data for (PPh4)2[Mo(CN)4O(amet)]3H2O, (PPh4)2[Mo(CN)4O(ampro)]3H2O and (PPh4)2[Mo(CN)4O(ethyd)] 3H2O respectively. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif of from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or e-mail: deposit@ccdc. cam.ac.uk. Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/ j.molstruc.2014.10.005. References [1] (a) S.J. Lippard, B.J. Russ, Inorg. Chem. 6 (1967) 1943–1947; (b) V.W. Day, J.L. Hoard, J. Am. Chem. Soc. 90 (1968) 3374–3379; (c) R. Schlupp, J.M. le Carpentier, R. Weiss, Revue de Chim. Miner. 7 (1970) 63– 74; (d) A. Samotus, M. Dudek, A. Kanas, J. Inorg. Nucl. Chem. 37 (1975) 943–948; (e) P.R. Robinson, E.O. Schlemper, R.K. Murmann, Inorg. Chem. 14 (1975) 2035– 2041; (f) M. Dudek, A. Kanas, A. Samotus, J. Inorg. Nucl. Chem. 42 (1980) 1701–1704; (g) K. Wieghardt, G. Backes-Dahmann, W. Holzbach, W.J. Swiridoff, J. Weiss, Z. Anorg, Allg. Chem. 499 (1983) 44–58; (h) S.S. Basson, J.G. Leipoldt, I.M. Potgieter, Inorg. Chim. Acta 87 (1984) 71–78; (i) M. Dudek, A. Samotus, Transition Met. Chem. 10 (1985) 271–274; (j) S.S. Basson, J.G. Leipoldt, I.M. Potgieter, A. Roodt, Inorg. Chim. Acta 103 (1985) 121–125; (k) J.P. Smit, W. Purcell, A. Roodt, J.G. Leipoldt, J. Chem. Soc. Chem. Commun. (1993) 1388–1389. [2] H. Arzoumanian, A. Bouraoui, V. Lazzeri, M. Rajzmann, H. Teruel, New J. Chem. 16 (1992) 965–972. [3] J. Szklarzewicz, A. Makuła, D. Matoga, J. Fawcett, Inorg. Chim. Acta. 358 (2005) 1749–1761. [4] D. Matoga, J. Szklarzewicz, A. Samotus, K. Lewin´ski, J. Chem. Soc., Dalton Trans. (2002) 3587–3592. [5] D. Matoga, J. Szklarzewicz, A. Samotus, J. Burgess, J. Fawcett, D.R. Russell, Polyhedron 19 (2000) 1503–1509. [6] (a) H. Arzoumanian, J.F. Petrignani, M. Pierrot, F. Ridouane, J. Sanchez, Inorg. Chem. 27 (1988) 3377–3381; (b) H. Arzoumanian, M. Pierrot, F. Ridouane, J. Sanchez, Transition Met. Chem. 16 (1991) 422–426; (c) J. Szklarzewicz, D. Matoga, A. Samotus, J. Burgess, J. Fawcett, D.R. Russell, Croatica Chem. Acta 74 (2001) 529–544. [7] See for example for Co complexes- (a) B.G. Gasanov, G.K. Abdullaev, Zh. Neorg. Khim. (Russ.) (Russ. J. Inorg. Chem.) 14 (1969) 1997; (b) J.A. Bertrand, F.T. Helm, L.J. Carpenter, Inorg. Chim. Acta 9 (1974) 69–75; (c) J. Jaciubek-Rosinska, M. Pajak, J. Jaszczak, M. Swiatek, I.O. Fritsky, Inorg. Chim. Acta 363 (2010) 2996–3003. [8] See for example for Co complexes- (a) P. Naumov, V. Jordanovska, M.G.B. Drew, S.W. Ng, Solid State Sci. 4 (2002) 455–460; (b) I.A. Guzei, L.C. Spencer, M.K. Ainooson, J. Darkwa, Acta Crystallogr. Sect. C: Cryst. Struct. Commun. 66 (2010) m89–m96. [9] (a) W.G. Ferrier, A.R. Lindsay, D.W. Young, Acta Crystallogr. 15 (1962) 616; (b) H.-P. Weber, R.K. McMullan, S. Swaminathan, B.M. Craven, Acta Crystallogr., Sect. B: Struct. Sci. 40 (1984) 506; (c) A.T. Myller, J.J. Karhe, M. Haukka, T.T. Pakkanen, J. Mol. Struct. 1033 (2013) 171; (d) Y. Okaya, Acta Crystallogr. 21 (1966) A124; (e) A.R.I. Munns, J.N. Low, P. Tollin, D.W. Young, Cryst. Struct. Commun. 10 (1981) 1431;
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Journal of Molecular Structure journal homepage: www.elsevier.com/locate/molstruc
N-substituted monodentate alcohols as ligands modifying structure, properties and thermal stability of Mo(IV) complexes Anna Jurowska a,⇑, Janusz Szklarzewicz a,⇑, Maciej Hodorowicz a, Monika Tomecka a, Janusz Lipkowski b, Wojciech Nitek a a b
Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Kraków, Poland Institute of Physical Chemistry of PAN, Kasprzaka 44, 01-224 Warsaw, Poland
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Three new Mo(IV) complexes with
monodentate ligands were synthesised. All complexes have been characterized by single crystal X-ray crystallography. Analysis, IR, UV–Vis, CV and DTG are presented and discussed.
a r t i c l e
i n f o
Article history: Received 12 September 2014 Received in revised form 2 October 2014 Accepted 2 October 2014 Available online 13 October 2014 Keywords: Molybdenum Aminoalcohols X-ray crystal structure Thermogravimetry Electronic spectra
a b s t r a c t The reaction of N-substituted alcohols (2-aminoethanol, 3-amino-1-propanol and 2-hydroxyethylhydrazine) with K3Na[Mo(CN)4O2]6H2O in water–ethanol solution results in isolation of three new complexes of formulae: (PPh4)2[Mo(CN)4O(amet)]3H2O (1), (amet = 2-aminoethanol), (PPh4)2[Mo(CN)4 O(ampro)]3H2O (2) (ampro = 3-amino-1-propanol) and (PPh4)2[Mo(CN)4O(ethyd)]3H2O (3) (ethyd = 2-hydroxyethylhydrazine). The isolated salts were characterized by elemental analysis, single crystal X-ray structure measurements, IR and UV–Vis spectroscopy and cyclic voltammetry. The complexes crystalize in triclinic space group with distorted octahedral geometry of the anion. The obtained salts belongs to a very rare group of complexes with monodentate terminal N-donating alcohols. The thermal stability is described for all complexes and compared with crystal structure parameters. Ó 2014 Elsevier B.V. All rights reserved.
Introduction They are very limited data with regard to the cyanido complexes of Mo(IV) with monodentate ligands of the ion formula [Mo(CN)4O(L)]n (where n = 2–4) [1]. The main type of L ligands are inorganic anions as CN , N3 , F , OH , O2 , H2O, HCN, NH3, little is known about organic ligands. The first isolated, in very drastic ⇑ Corresponding authors. Tel.: +48 12 6632223; fax: +48 12 6340515. E-mail addresses: [email protected] (A. Jurowska), szklarze@chemia. uj.edu.pl (J. Szklarzewicz). http://dx.doi.org/10.1016/j.molstruc.2014.10.005 0022-2860/Ó 2014 Elsevier B.V. All rights reserved.
conditions, were with L = aliphatic diamines (as etylenediamine, propylenediamine, and other ligands) bonded in monodentate way [2]. The complexes with 2-pyridinecarboxaldehyde, pyridine and pyrazine in water–ethanol solutions were also synthesized [3–5]. The main problem connected with such synthesis is a very weak bonding of organic ligands, being in trans position to a very short Mo@O bond. Moreover, the complexes have to be isolated as their tetraphenylphosphonium salts as the alkali metal salts are too basic and decomposition of these complexes is observed. On the other hand, tetraphenylphosphonium salts were found to be very reactive both in solution and in solid state, for example
A. Jurowska et al. / Journal of Molecular Structure 1081 (2015) 6–13
they react with molecular oxygen with formation of peroxo complexes with the anion formula [Mo(CN)4O(O2)]2 , molybdenum is oxidized to +6 formal oxidation state [6]. In present paper we decided to extend our knowledge on complexes with ligands possessing amino and hydroxyl group. As ligands we used 2-aminoethanol, 3-amino-1-propanol and 2hydroxyethylhydrazine. The structure of compounds with 2hydroxyethylhydrazine have not yet been described up to our knowledge. The 2-aminoethanol and 3-amino-1-propanol can be coordinated to a metal center both as N- or O-donating ligands. As monodentate ligands they can be coordinated by nitrogen [7] or oxygen atom [8] even for the same metal center, in summary 43 structures of such a coordination mode were described [9]. For metal complexes 19 are with MeAN, while only 10 with MeAO as donor atom. Much more often 2-aminoethanol and 3-amino-1-propanol acts as bidentate ligand [10] or even tridentate [11]. In this paper we obtained complexes with only monodentate N-donating ligands. This gave us unique possibility to study the intermolecular interactions and to compare the physicochemical properties of complexes with different R substituents in L ligand of general formula H2NARAOH. The thermal stability is drown from the intermolecular interactions present in solid state. These data are of special interest as all complexes belongs to a very rare class in which the formula is almost identical, salts are isostructural, poses the same number of hydration waters, similar hydrogen bonds net and only difference is that amino alcohols ligands differs by NH2AOH distance (from CAC, CACAC to NHACAC separation). This allows us for a very precise correlation between structure and thermal stability. Experimental Materials and methods K3Na[Mo(CN)4O2]6H2O was synthesized according to published methods [1d]. All other chemicals were of analytical grade (Aldrich) and were used as supplied. Microanalysis of carbon, hydrogen and nitrogen were performed using Elementar Vario MICRO Cube elemental analyzer. Thermogravimetric analysis were performed on a TGA/SDTA 851e Mettler Toledo apparatus. The studied complexes were placed in open alumina crucibles (150 ll) and were heated from 25 to 650 °C with constant heating rate 10 °C/min under Ar flow (80 ml/min). The temperature was measured by a Pt–Pt/Rh thermocouple with the accuracy of ±0.5 °C. Solid samples for IR spectroscopy were recorded on a Nicolet iS5 FT-IR spectrophotometer. The electronic absorption spectra were recorded with Shimadzu UV-3600 UV–VIS–NIR spectrophotometer equipped with a CPS-240 temperature controller. Diffuse reflectance spectra were measured in BaSO4 pellets with BaSO4 as a reference on Shimadzu 2101PC equipped with an ISR-260 integrating sphere attachment. Cyclic voltammetry measurements were carried out in MeCN (acetonitrile) with [Bu4N]PF6 (0.1 M) as the supporting electrolyte, using Pt working and counter and Ag/AgCl reference electrodes on an AUTOLAB/PGSTAT 128 N Potentiostat/Galvanostat. E1/2 values were calculated from the average anodic and cathodic peak potentials, E1/2 = 0.5 (Ea + Ec). The redox potentials were calibrated versus ferrocene (0.440 V versus SHE), which was used as an internal potential standard for measurements in organic solvents to avoid the influence of a liquid junction potential; the final values are reported versus the standard hydrogen electrode (SHE). Synthesis of (PPh4)2[Mo(CN)4O(L)]3H2O, L = amet, ampro and ethyd (1–3) The complexes (PPh4)2[Mo(CN)4O(amet)]3H2O (1), (PPh4)2[Mo(CN)4O(ampro)]3H2O (2) and (PPh4)2[Mo(CN)4
7
O(ethyd)]3H2O (3) were synthesized in water–ethanol solutions. All three ligands: 2-aminoethanol, 3-amino-1-propanol and 2-hydroxyethylhydrazine (10 mmol) were dissolved in 10 ml of ethanol and heated to 40 °C for several minutes. The solution of K3Na[Mo(CN)4O2]6H2O (1 mmol) in 20 ml of water was added to these three ligands separately. Then solid PPh4Br (1 mmol) was added and the obtained blue crystals were filtered off, washed with the water and dried in air at room temperature. The yields are: 58%, 42% and 67% for 1, 2 and 3 respectively. The Anal. Calcd. for C54H53MoN5O5P2 (1): C, 64.29; H, 5.20; N, 6.94%. Found: C, 64.55; H, 5.25; N, 6.91%, Anal. Calcd. for C55H55MoN5O5P2 (2): C, 64.58; H, 5.32; N, 6.85%. Found: C, 64.86; H, 5.22; N, 6.78% and Anal. Calcd. for C54H54MoN6O5P2 (3): C, 63.28; H, 5.31; N, 8.20%. Found: C, 63.25; H, 5.39; N, 8.36%. Crystallographic data collection and structure refinement Diffraction data for single crystal of (PPh4)2[Mo(CN)4O(amet)]3H2O (1), (PPh4)2[Mo(CN)4O(ampro)]3H2O (2) and (PPh4)2[Mo(CN)4O(ethyd)]3H2O (3) were collected at 140, 100 and 293 K for 1, 2 and 3 respectively on the Oxford Diffraction SuperNova four circle diffractometer, using the Cu (1.54180 Å) for 1 and Mo (0.71069 Å) for 2 and 3 Ka radiation source and graphite monochromator. Cell refinement and data reduction was performed using firmware [12]. Positions of all of non-hydrogen atoms were determined by direct methods using SIR-97 [13]. All non-hydrogen atoms were refined anisotropically using weighted full-matrix least-squares on F2. Refinement and further calculations were carried out using SHELXL-97 [14]. Moreover, several restraints, such as EDAP, SIMU, DELU and ISOR, were applied to deal with the disordered atoms or groups. All hydrogen atoms joined to carbon atoms were positioned with an idealized geometry and refined using a riding model [with Uiso(H) fixed at 1.5 Ueq of C for methyl groups and 1.2 Ueq of C for other] whereas hydrogen atoms of AOH, ANH2 groups were included from the difference maps and were refined with isotropic thermal parameters. In the structure 1 at the oxygen atom O(13) (water molecule) is unable to find the hydrogen atoms from difference Fourier map. The 2aminoethanol group (in 1) coordinated to molybdenum atom is disordered and all atoms N5, C6, C7 and O2 were refined in two complementary positions. Additionally the bond lengths N5A– O2A and N5B–O2B were restrained during refinement to preserve proper geometry. Results and discussion Description of crystal structures Compounds 1 and 2 are isostructural with 3. Single-crystal Xray study reveals that the asymmetric part of the unit cells of the complexes 1, 2 and 3 have similar stoichiometry: [Mo(CN)4O(L)]2 anion, L = 2-aminoethanol (1), 3-amino-1-propanol (2), 2-hydroxyethylhydrazine (3), two PPh+4 cations and three water molecules of solvation (Fig. 1a–c). The crystallographic data and detailed information on the structure solution and refinement for 1, 2 and 3 are given in Table 1 and Table S1 in Supporting information. Although the measurement was held in 140 K, the ethanolamine ligand (1), shows a dynamic disorder (labeled as N5A–O2A and N5B–O2B). One of the three water molecules for structures 2 and 3, H2O(16), shows static disorder and consequently partial occupancy (site occupancy factor 0.63 and 0.75 for 2 and 3 respectively). In all three structures the [Mo(CN)4O]2 moiety adopts the same conformation in that the cyanido ligands are arranged in an equatorial square plane (the coordinated Mo(1) atom is located
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Fig. 1. Single-crystal X-ray structure of 1, 2 and 3 showing the atom labeling scheme and 30% displacement ellipsoids.
Table 1 Crystal data and structure refinement parameters for 1, 2 and 3.
Empirical formula Formula weight Crystal size (mm) Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) h k l V (Å3) Z T (K) Dx (Mg/m3) Reflections collected Independent reflections Final R indices [I > 2sigma(I)] R indices (all data) Goodness-of-fit on F2
1
2
3
C54H51MoN5O5P2 1007.88 0.42 0.26 0.07 Triclinic P1
C55H54.25 Mo N5O4.63 P2 1017.18 0.200 0.200 0.200 Triclinic P1
C54H53.50MoN6O4.75P2 1024.40 0.230 0.140 0.080 Triclinic P1
13.377(5) 13.821(5) 16.326(5) 109.018(5) 90.799(5) 118.683(5) 16 to 16 16 to 16 19 to 20 2450.10(15) 2 140 1.366 36,548 18,986 [R(int) = 0.0217] R1 = 0.0312, wR2 = 0.0791
13.422(3) 13.744(4) 16.505(4) 70.286(2) 89.707(2) 61.640(3) 17 to 18 18 to 18 22 to 22 2477.45(13) 2 100 1.364 42,304 9,391 [R(int) = 0.0328] R1 = 0.0257, wR2 = 0.0647
13.5844(5) 13.9093(5) 16.6740(6) 110.019(3) 90.163(3) 118.842(4) 18 to 18 18 to 17 22 to 22 2538.40(19) 2 293 1.340 37,060 11,876 [R(int) = 0.0432] R1 = 0.0490, wR2 = 0.1038
R1 = 0.0359, wR2 = 0.0824 1.019
R1 = 0.0286, wR2 = 0.0666 1.024
R1 = 0.0876, wR2 = 0.1344 1.098
at 0.445(1) Å for 1, 0.586(1) Å for 2 and 0.449(2) Å for 3 over the cyanido N4 plane, Fig. 1a) with an average MoAC distances 2.164 Å for 1, 2.163 Å for 2 and 2.159 Å for 3. These distances are typical for complexes with monodentate N-donating ligands [1]. An average OAMoAC bond angles are 100,15°, 100,35° and 100,23° for 1, 2 and 3 respectively and are very similar to these found in other complexes of Mo(IV) with monodentate N-donating ligands e.g. the average bond angles are: 100,78° for NH3 ligand [15], 101,63° for ethylenediamine (en) ligand [2], 100,68° for 2pyrazinecarbonitrile (pcn) ligand [16] and 101,20° for HCN ligand [1b]. The oxo ligand in axial position (the apex of a square pyramid) is significantly closer to molybdenum(IV) ion than four cyanido groups and it forms short Mo@O bond (1.676(2) Å for 1, 1.681(1) Å for 2 and 1.658(2) Å for 3). The interatomic bond distances of Mo@O are comparable with other characterized cyanidooxocomplexes of molybdenum(IV) with monodentate ligands. For (PPh4)2[Mo(CN)4O(NH3)]2H2O this distance is 1.661 Å [15], for complex with en 1.666 Å [2], with pyrazine (pz) 1.662 Å [4], with pcn 1.653 Å [16] and with HCN ligand 1.655 Å [1b]. All these bonds are relatively short and can be treated as a triple bond (Mo„O 1.65 Å) according to the Cotton classification [17].
Additionally in position trans to the oxo ligand, N-substituted alcohol (L) molecule is located, L = 2-aminoethanol for 1, 3amino-1-propanol for 2 and 2-hydroxyethylhydrazine for 3. These molecules form relatively long Mo–N5 bond (2.426(5), 2.412(1) and 2.401(3) Å for 1, 2 and 3 respectively) and they are similar to bond length observed in complex with NH3 and HCN ligands (2.422 and 2.435 Å respectively) [15,1b]. Considerably longer analogous MoAN bond has been observed in complexes with en ligand (2.491 Å) [2], with pz ligand (2.569 Å) [4] and with pcn ligand (2.538 Å) [16]. These differences in lengths of coordination bond cause the distortion of coordination octahedron (Table S1 in Supporting information). In complexes with another than molybdenum metal center (e.g. Cu and Fe) and with 2-aminoethanol or 3-amino-1-propanol as N-donating ligand, these distances are much shorter, e.g. CuAN is 2.038 Å (for complex with 2-aminoethanol) [18] and FeAN is 2.021 Å (for complex with 3-amino-1-propanol) [19]. Only for Pb complex with 2-aminoethanol the PbAN distance is also long (2.554 or 2.564 Å) due to radius of Pb ion [20]. Analysis of the crystal structure of 1, 2 and 3 at the supramolecular level reveals that the complex molecules are held together by two T-shape hydrogen CAH p and OAH p bondings (Fig. 2) and
A. Jurowska et al. / Journal of Molecular Structure 1081 (2015) 6–13
9
Fig. 2. The CAH p bonds in 2.
Fig. 3. The hydrogen bonds in 2. The cations are omitted for clarity.
several hydrogen interactions (Fig. 3), which are summarized in Tables S2–S5 in Supporting information. The XAH p contact can be classified by type IV, according to Malone [21]. The crystal contains inorganic coordination chains running along the c direction, in which the structural unit containing two neighboring Mo(IV) ions linked (see Fig. 3). The lattice water molecules participates in many hydrogen bonds of OAH O and OAH N type linking belonging to the structural units of adjacent ribbons (Fig. 3). The water molecules at (x, y, z) participate in O(14)AH(14A) O(15)[x + 1,y,z] and O(15)AH(15B) O(14)[ x,+1y, z+2] hydrogen bonds, forming small R44(8) rings [22]. All these interactions are responsible for self-assembly of the complexes molecules and stabilization of 3D structures. The shortest intermolecular Mo Mo distances are 8.907(2) Å, 9.555(2) Å, 9.474(4) Å for 1, 2 and 3 respectively.
IR spectra In the infrared spectra the mMo@O band positions in 1, 2 and 3 (964, 960 and 964 cm 1, respectively) are in the range typical for analogous [Mo(CN)4O(L)]n complexes, where L can be N-donor ligands [1] (see Fig. 4). In all three complexes the bands located at 2091, 2103, 2115 cm 1 for 1, at 2088, 2104, 2119 cm 1 for 2 and at 2091, 2104, 2119 cm 1 for 3 are observed and can be assigned to the vibration connected with cyanido ligands. The similar situation is observed for the Cs2Na[Mo(CN)5O] and (PPh4)2 [Mo(CN)4O(py)]2H2O (py = pyridine) complexes, where these bands are located at 2064, 2108, 2122 cm 1 and at 2089, 2098, 2111 cm 1 respectively [1a,4]. In literature it was found, that in complexes with monodentate ligands except three bands, one, two or even four cyanido bands can be observed. For
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Fig. 4. The ATR-FTIR spectra of 1 (black line), 2 (red line) and 3 (blue line). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Fig. 7. Cyclic voltammogram of 1 in MeCN and 0.1 M Bu4NPF6 as electrolyte. In the upper left corner voltammograms recorded at different scan speeds are shown.
Table 2 Cyclic voltammetry data.
Fig. 5. UV–Vis spectra of 1 in EtOH and DMSO (dotted line).
Fig. 6. UV–Vis reflectance spectra of 1 (black line), 2 (red line) and 3 (blue line) in BaSO4 after Kubelka–Munk transformation. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
V (mV/s)
Ea1 (V)
Ea2 (V)
Ek1 (V)
20 50 100 200 500 1000
0.260 0.262 0.272 0.277 0.314 0.320
0.372 0.376 0.391 0.397 – –
– – – – 0.152 0.153
Ek2 (V) 0.023 0.018 0.002 0.012 0.024 0.038
DV (Ea1
Ek1) (V)
– – – – 0.162 0.167
(PPh4)2[Mo(CN)4O(pcn)]2H2O (pcn = 2-pyrazinecarbonitrile) only one band at 2091 cm 1 appeared [16], for (PPh4)2[Mo(CN)4O(NH3)] two bands at 2084 and 2110 cm 1 are observed [15] and for (PPh4)2[Mo(CN)4O(pz)]3H2O (pz = pyrazine) four bands are located at 2085, 2088, 2094 and 2103 cm 1 [5]. The number of bands in the region characteristic for vibration of cyanido ligands depends on an anion symmetry and specific position of CN versus L ligands. Salts 1, 2 and 3 are isostructural and cyanido ligands location is almost similar, thus all three complexes have the same number of the cyanido bands. The band at 3657 cm 1 is connected with the stretching of the hydroxyl group of monodentate ligands. In the other regions, at 1100 and 997 cm 1 the bands typical for PPh4 cation are observed for all three compounds.
Fig. 8. TG and DTG curves for complex 1.
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Cyclic voltammetry measurements The recorded cyclic voltammogram for 1 is presented on Fig. 7 while the data are presented in Table 2. Two oxidation peaks at 0.272 and 0.391 V and one reduction peak at 0.002 V are observed (at 100 mV/s). The complexes with monodentate ligands are unstable in solutions, as it was seen on Fig. 7, with L ligand exchange into solvent molecule, thus cyclic voltammograms of all salts 1, 2 and 3 are similar. In general two oxidation peaks are observed: the peak at lower potential can be assigned to [Mo(CN)4 O(L)] /2 (L = solvent) and the second peak is connected with redox system of the decomposition products of oxidized [Mo(CN)4O(L)]2 molecule. Detailed study of the process, at various scan speed (Fig. 7) shows, that the peak position is only merely dependent on the scan speed and at 500 mV/s the reduction peak starts to be observed. Such behavior is typical for reversible redox process, in which, after oxidation, the compound undergoes chemical reactions.
Fig. 9. TG and DTG curves for complex 2.
Thermogravimetry
Fig. 10. TG and DTG curves for complex 3.
UV–Vis spectra The UV–Vis measurements shows that the complexes release L ligand in solutions with formation of [Mo(CN)4O(solv)]2 ion (Fig. 5). Thus only the reflectance spectra can give proper energy of d–d transitions observed in visible part of the spectra (see Fig. 6). The very close similarity of ligands L in 1, 2 and 3 is reflected in d–d band positions, which are 638, 626 and 623 nm for 1, 2 and 3 respectively.
The TG and DTG curves for the hydrated complexes 1–3 are shown in Figs. 8-10 respectively. The numerical data are collected in Table 3. For all salts similar decomposition pattern is observed. In the first step water of hydration is released, then organic ligand (for salts 1 and 2 this decomposition is overlapped with partial cation release) and finally the cations. At higher temperatures than 500 °C also cyanido ligands are released. This can be especially well seen for salt 1, where TG up to 1000 °C was measured (the measurement above 650 °C were performed only for 1 as measurements above 650 °C are dangerous for apparatus as MoO3 can start to sublimate). Moreover under Ar atmosphere it is difficult to get well defined product of molybdenum complexes decomposition (in most cases mixture of MoO3 and molybdenum carbides is observed). The observed DTG peaks indicate that the lowest decomposition temperature is for salt 2, then for 3 and 1. The detailed study of the hydrogen bond distances indicate that this order is reflected in the bond lengths between cyanide nitrogen and hydroxyl oxygen (2.752, 2.746 and 2.739 Å respectively for 2, 3 and 1) and is not reflected in any other order of hydrogen bond distances involving water molecules. As shown in Fig. 11, this bond keeps two anions together. It seems, that order of DTG maxima suggests that the dehydration of salts 1–3 starts from NAO bond breaking, which breaks anion – anion interaction. Above and below the presented in
Table 3 Thermal data for the decomposition of complexes 1–3. Complex
Temp. range (°C)
DTG peak (°C)
Obs. wt. loss Dm/m (%)
Calc. wt. loss Dm/m (%)
Evolution of
1
25–138 138–208 208–313 313–583 583–733 733–1000 5–171 171–306 306–383 383–608 25–119 119–147 147–205 205–319 319–419 419–562 562–646
97.7 203.0 293.0 326.0 669.0 – 89.2 283.3 318.3 401.2 92.2 131.7 195.8 296.2 334.2 440.5 –
4.81 8.66 36.46 76.34 82.27 84.14 6.54 36.59 70.68 81.60 3.80 6.14 10.42 34.08 70.08 75.57 77.77
5.36 8.38 36.30 78.68 81.36 84.04 5.31 36.68 70.01 81.99 3.51 5.27 12.69 35.85 70.27 76.89 78.88
3H2O 0.5 amet 0.5 amet, 0.74 PPh4 1.26 PPh4 HCN HCN 3H2O ampro, 0.72 PPh4 PPh4 0.28 PPh4, HCN 2H2O H2O ethyd 0.7 PPh4 1.04 PPh4 0.2 PPh4 0.06 PPh4
2
3
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Fig. 11. The hydrogen bonds in 1, 2 and 3.
Fig. 11 member ring (MoACNAligand’AMo’ACN’AligandAMo, where ligand denote amet, ampro or ethyd) the perpendicular phenolic rings of PPh+4 cations are presented. After breaking the hydrogen bonds, they can separate anions and in effect causes the collapse of the structure. The water of hydration now can be easily removed. There is no correlation between MoAN (from organic ligand) bond length and DTG maximum position for organic ligand release. The DTG maxima are at 203, 283 and 195 °C, while the MoAN bond lengths are 2.426(1), 2.412(2) and 2.401(3) Å for 1, 2 and 3 respectively. This is expected feature, as hydrogen bonds affect the MoAN distance. When hydroxyl group of ligand becomes ‘‘free’’ the MoAN distance change and as a result there is no direct correlation between DTG maxima position and structural data. After alcohol release, the Mo(IV) becomes unsaturated and decomposition of complex accompanied by redox processes starts. This is responsible for partial cation release, and at higher temperatures for cyanido ligands (probably in form of HCN or (CN)2) release. Conclusions The aminoalcohols are often used and they can serve as selfadopting to metal center multidentate ligands. In the most cases, they form bonds with typical metal-nitrogen distance, similar to that in other amines as ligands. In complexes 1–3 the MoAN distance is in contrary very long, nevertheless for these N-substituted alcohols influence on complex properties still can be well recognized. All studied salts 1–3 are isostructural, have the same numbers of cations and water of hydration, have the same metal arrangement. However, even for very geometrically similar ligands in 2 and 3 specific ligand effect is observed. For example the MoAN bond distance changes in order 1 > 2 > 3, Mo@O bond (trans to MoAN) changes in order 2 > 1 > 3, while the mMo@O changes in order 1 = 3 > 2. This, as found by structural study, is not an effect of steric hindrances, but rather should be interpreted as specific electronic effect. This is especially well seen for hydrazine analogue in 3, where change of carbon atom into nitrogen one results in change of physicochemical properties. The most striking is the position of the d–d bands in electronic spectra, supporting the specific electronic ligand effect. The specific ligand effect is also strongly reflected in thermogravimetric measurements. Although the TG curves look different for all salts, the decomposition patter is very similar. The DTG maxima positions for 1–3 indicate that the dehydration process starts from cyanide nitrogen–oxygen from hydroxyl group hydrogen bond breaking. This process breaks anion–anion interaction what yields the structure collapse and as a result water of hydration can be removed. Acknowledgements The research was carried out partially with the equipment purchased thanks to the financial support of the European Regional Development Fund in the framework of the Polish Innovation Economy Operational Program (Contract No. POIG.02.01.00-12023/08).
This work was made by the scholarship support of the first author by the Krakow Marian Smoluchowski Consortium ‘‘Matter–Energy–Future’’ (KNOW grant). Appendix A. Supplementary material CCDC 1002391, 1002392 and 1002393 contains the supplementary crystallographic data for (PPh4)2[Mo(CN)4O(amet)]3H2O, (PPh4)2[Mo(CN)4O(ampro)]3H2O and (PPh4)2[Mo(CN)4O(ethyd)] 3H2O respectively. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif of from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or e-mail: deposit@ccdc. cam.ac.uk. Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/ j.molstruc.2014.10.005. References [1] (a) S.J. Lippard, B.J. Russ, Inorg. Chem. 6 (1967) 1943–1947; (b) V.W. Day, J.L. Hoard, J. Am. Chem. Soc. 90 (1968) 3374–3379; (c) R. Schlupp, J.M. le Carpentier, R. Weiss, Revue de Chim. Miner. 7 (1970) 63– 74; (d) A. Samotus, M. Dudek, A. Kanas, J. Inorg. Nucl. Chem. 37 (1975) 943–948; (e) P.R. Robinson, E.O. Schlemper, R.K. Murmann, Inorg. Chem. 14 (1975) 2035– 2041; (f) M. Dudek, A. Kanas, A. Samotus, J. Inorg. Nucl. Chem. 42 (1980) 1701–1704; (g) K. Wieghardt, G. Backes-Dahmann, W. Holzbach, W.J. Swiridoff, J. Weiss, Z. Anorg, Allg. Chem. 499 (1983) 44–58; (h) S.S. Basson, J.G. Leipoldt, I.M. Potgieter, Inorg. Chim. Acta 87 (1984) 71–78; (i) M. Dudek, A. Samotus, Transition Met. Chem. 10 (1985) 271–274; (j) S.S. Basson, J.G. Leipoldt, I.M. Potgieter, A. Roodt, Inorg. Chim. Acta 103 (1985) 121–125; (k) J.P. Smit, W. Purcell, A. Roodt, J.G. Leipoldt, J. Chem. Soc. Chem. Commun. (1993) 1388–1389. [2] H. Arzoumanian, A. Bouraoui, V. Lazzeri, M. Rajzmann, H. Teruel, New J. Chem. 16 (1992) 965–972. [3] J. Szklarzewicz, A. Makuła, D. Matoga, J. Fawcett, Inorg. Chim. Acta. 358 (2005) 1749–1761. [4] D. Matoga, J. Szklarzewicz, A. Samotus, K. Lewin´ski, J. Chem. Soc., Dalton Trans. (2002) 3587–3592. [5] D. Matoga, J. Szklarzewicz, A. Samotus, J. Burgess, J. Fawcett, D.R. Russell, Polyhedron 19 (2000) 1503–1509. [6] (a) H. Arzoumanian, J.F. Petrignani, M. Pierrot, F. Ridouane, J. Sanchez, Inorg. Chem. 27 (1988) 3377–3381; (b) H. Arzoumanian, M. Pierrot, F. Ridouane, J. Sanchez, Transition Met. Chem. 16 (1991) 422–426; (c) J. Szklarzewicz, D. Matoga, A. Samotus, J. Burgess, J. Fawcett, D.R. Russell, Croatica Chem. Acta 74 (2001) 529–544. [7] See for example for Co complexes- (a) B.G. Gasanov, G.K. Abdullaev, Zh. Neorg. Khim. (Russ.) (Russ. J. Inorg. Chem.) 14 (1969) 1997; (b) J.A. Bertrand, F.T. Helm, L.J. Carpenter, Inorg. Chim. Acta 9 (1974) 69–75; (c) J. Jaciubek-Rosinska, M. Pajak, J. Jaszczak, M. Swiatek, I.O. Fritsky, Inorg. Chim. Acta 363 (2010) 2996–3003. [8] See for example for Co complexes- (a) P. Naumov, V. Jordanovska, M.G.B. Drew, S.W. Ng, Solid State Sci. 4 (2002) 455–460; (b) I.A. Guzei, L.C. Spencer, M.K. Ainooson, J. Darkwa, Acta Crystallogr. Sect. C: Cryst. Struct. Commun. 66 (2010) m89–m96. [9] (a) W.G. Ferrier, A.R. Lindsay, D.W. Young, Acta Crystallogr. 15 (1962) 616; (b) H.-P. Weber, R.K. McMullan, S. Swaminathan, B.M. Craven, Acta Crystallogr., Sect. B: Struct. Sci. 40 (1984) 506; (c) A.T. Myller, J.J. Karhe, M. Haukka, T.T. Pakkanen, J. Mol. Struct. 1033 (2013) 171; (d) Y. Okaya, Acta Crystallogr. 21 (1966) A124; (e) A.R.I. Munns, J.N. Low, P. Tollin, D.W. Young, Cryst. Struct. Commun. 10 (1981) 1431;
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