Synthesis and structural analysis of cis-bis(1,10-phenanthroline)dicarbonyl ruthenium(II) 1.72-trifluoromethanesulfonate 0.28-hexafluoridophosphate European Journal of Chemistry 12 (4) (2021) 389-393 European Journal of Chemistry ISSN 2153-2249 (Print) / ISSN 2153-2257 (Online) – Copyright © 2021 The Authors – Atlanta Publishing House LLC – Printed in the USA. This work is published and licensed by Atlanta Publishing House LLC – CC BY NC – Some Rights Reserved. https://dx.doi.org/10.5155/eurjchem.12.4.389-393.2151 European Journal of Chemistry View Journal Online View Article Online Synthesis and structural analysis of cis-bis(1,10-phenanthroline)dicarbonyl ruthenium(II) 1.72-trifluoromethanesulfonate 0.28-hexafluoridophosphate Tsugiko Takase and Dai Oyama * Department of Natural Sciences and Informatics, Fukushima University, 1 Kanayagawa, Fukushima, 960-1296, Japan ttakase@sss.fukushima-u.ac.jp (T.T.), daio@sss.fukushima-u.ac.jp (D.O.) * Corresponding author at: Department of Natural Sciences and Informatics, Fukushima University, 1 Kanayagawa, Fukushima, 960-1296, Japan. e-mail: daio@sss.fukushima-u.ac.jp (D. Oyama). 10.5155/eurjchem.12.4.389-393.2151 Received: 15 July 2021 Received in revised form: 20 August 2021 Accepted: 28 August 2021 Published online: 31 December 2021 Printed: 31 December 2021 Ruthenium(II) complexes containing both 1,10-phenanthroline (Phen) and carbonyl (CO) ligands are important molecules for various applications including catalysis. In this work, the molecular structure of [Ru(Phen)2(CO)2]2+ was determined via X-ray diffraction analysis for the first time. The complex exhibits substitutional disorder of one of counter-anions in the asymmetric unit, with different occupancies for CF3SO3 − (0.72) and PF6 − (0.28). The ruthenium atom is coordinated in a distorted octahedral environment by two carbonyl carbon atoms and four nitrogen atoms from bis-Phen ligands. The cation displays a cis configuration of the carbonyl ligands. Several hydrogen bonds and π-π interactions are present in the crystal. In addition to structural characterization, IR spectral data for the complex is compared with calculated values. These results provide fundamental data for understanding various properties of related ruthenium complexes. Carbonyl IR spectra Crystal structure Ruthenium complex 1,10-Phenanthroline Computational chemistry Cite this: Eur. J. Chem. 2021, 12(4), 389-393 Journal website: www.eurjchem.com 1. Introduction 1,10-Phenanthroline has been used as a rigid and planar bidentate chelate ligand (Figure 1a). In particular, because of its similarities in structure and properties to 2,2'-bipyridine (Bpy; Figure 1b), numerous catalytic, redox, photochemical, and photophysical properties have been studied in metal complexes containing those ligands [1]. In the cis-[RuL2(CO)2]2+ (L = Bpy or Phen) complexes shown in Figure 1c, some ligand effects regarding electrochemical CO2 reductions and reactivities have been compared [2,3]. Thus, the comparison of properties between Bpy-containing complexes and Phen-containing ones is an important area of research. Although the structural analysis of [Ru(Bpy)2(CO)2]2+ was reported approximately thirty years ago [4], to the best of our knowledge, no structural determination of [Ru(Phen)2(CO)2]2+ has been performed. Therefore, direct structural comparisons between the dyad have not been studied, despite the great interest in these comparisons. This study reports the single crystal X-ray structural analysis of [Ru(Phen)2(CO)2]2+. We compare not only the structural data with previously reported analyses of similar complexes but also the spectroscopic data of the title compound with calculated data derived from computational chemistry. N N N N Ru OC OC N N N N L L (a) (b) (c) Figure 1. Chemical structures of (a) 1,10-phenanthroline (Phen), (b) 2,2ʹ- bipyridine (Bpy), and (c) cis-[RuL2(CO)2]2+ (L = Phen or Bpy). 2. Experimental 2.1. Measurements IR spectra were measured as KBr pellets using a JASCO FT- IR 4100 spectrometer. Electrospray ionization mass spectro- metry (ESI-MS) data were obtained using a Bruker Daltonics micrOTOF spectrometer. 1H NMR spectra were acquired using a JEOL JMN-AL300 spectrometer operating at 1H frequency of 300 MHz. The formation of the title compound was confirmed by conducting spectroscopic measurements [2]. ABSTRACT RESEARCH ARTICLE KEYWORDS https://dx.doi.org/10.5155/eurjchem.12.4.389-393.2151 https://www.eurjchem.com/ https://dx.doi.org/10.5155/eurjchem.12.4.389-393.2151 mailto:ttakase@sss.fukushima-u.ac.jp mailto:daio@sss.fukushima-u.ac.jp mailto:daio@sss.fukushima-u.ac.jp http://www.eurjchem.com/ https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.12.4.389-393.2151&domain=pdf&date_stamp=2021-12-31 390 Takase and Oyama / European Journal of Chemistry 12 (4) (2021) 389-393 2021 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.12.4.389-393.2151 Table 1. Crystal data and details of the structure refinement for the complex. Empirical formula C27.72H16F6.83N4O7.17P0.28RuS1.72 Formula weight 814.52 Temperature (K) 113(2) Crystal system Monoclinic Space group P21/c a, (Å) 13.0106(2) b, (Å) 17.5914(3) c, (Å) 12.8315(2) α (°) 90 β (°) 92.9715(7) γ (°) 90 Volume (Å3) 2932.85(9) Z 4 ρcalc (g/cm3) 1.845 μ (mm-1) 0.772 F(000) 1620.0 Crystal size (mm3) 0.150 × 0.150 × 0.100 Radiation MoKα (λ = 0.71075) 2Θ range for data collection (°) 6.272 to 54.968 Index ranges -16 ≤ h ≤ 16, -22 ≤ k ≤ 22, -16 ≤ l ≤ 16 Reflections collected 30123 Independent reflections 6728 [Rint = 0.0181, Rsigma = 0.0138] Data/restraints/parameters 6728/0/471 Goodness-of-fit on F2 0.997 Final R indexes [I≥2σ (I)] R1 = 0.0268, wR2 = 0.0693 Final R indexes [all data] R1 = 0.0299, wR2 = 0.0711 Largest diff. peak/hole (e.Å-3) 0.39/-0.44 Density functional theory (DFT) calculations were perfor- med using the quantum chemical program, Gaussian 16 [5]. The geometries of the complex were fully optimized using restricted DFT methods employing the B3LYP function [6,7], with a 6- 31G(d) basis set for the light elements [8,9] and a LanL2DZ basis set [10] for the Ru atom. Vibrational analyses were performed at the same calculation level employed for geometry optimization. 2.2. Synthesis of the complex All solvents for the synthesis were anhydrous and used without further purification. Ruthenium trichloride was purchased from Furuya Metal Co. Inc. [Ru(CO)2Cl2]n and cis- [Ru(Phen)(CO)2(OH2)2](CF3SO3)2 were prepared according to previously reported procedures [11,12]. [Ru(Phen)(CO)2 (OH2)2](CF3SO3)2 (39 mg, 0.10 mmol) and Phen (21 mg, 0.10 mmol) were added to ethanol (20 mL). The mixture was refluxed with stirring for 1.5 h. The reaction vessel was cooled to room temperature. The reaction mixture was condensed to 3 mL under reduced pressure and was then cooled to 4 °C and allowed to stand overnight. The addition of diethyl ether (20 mL) to the solution resulted in the formation of a precipitate. The product was collected via filtration, washed with cold water and diethyl ether, and dried in vacuo to produce 41 mg of [Ru(Phen)2(CO)2](CF3SO3)2 (50% yield). ESI-MS (CH3CN, m/z): 259.0 ([M]2+). 1H NMR (300 MHz, Acetone-d6, δ, ppm): 10.04 (dd, J = 5.1, 1.2 Hz, 2H, Ar-H), 9.31 (dd, J = 8.4, 1.2 Hz, 2H, Ar-H), 8.93 (dd, J = 8.4, 1.5 Hz, 2H, Ar-H), 8.56-8.49 (m, 4H, Ar-H), 8.43 (d, J = 9.0 Hz, 2H, Ar-H), 8.13 (dd, J = 5.7, 1.2 Hz, 2H, Ar-H), 7.81 (dd, J = 8.1, 5.4 Hz, 2H, Ar-H). 2.3. Crystallography Single crystals suitable for X-ray diffraction analysis were obtained via vapor diffusion of diethyl ether into an acetone solution of the complex and a small amount of methanolic solution of NH4PF6 over the course of a few days. A single crystal of the title compound was analyzed using a Rigaku Saturn70 CCD diffractometer. The crystal was kept at 113 K during the data collection. All calculations were performed using Crystal Structure [13] except for the refinement, which was performed using SHELXL2018/3 [14]. The non-hydrogen atoms, with the exception of PF6−, were anisotropically refined. All hydrogen atoms bonded to carbon atoms were positioned geometrically and refined as a riding model. The counter-anion sites were refined as being substitutionally disordered between trifluoro methanesulfonate and hexafluoridophosphate, with an occu- pancy of 0.723(3) for CF3SO3− and 0.277(3) for PF6−. Crystallo- graphic data are summarized in Table 1. 3. Results and discussion 3.1. Crystallization and structure Initially, we prepared the title compound as a hexafluorido phosphate (PF6) salt, as per a previously reported procedure [2]. Although we tried, we could not obtain any single crystals of the compound suitable for X-ray diffraction experiments. Therefore, we developed the title compound via another route, which involved the reaction of the mono-Phen precursor, cis(OH2)-[Ru(Phen)(CO)2(OH2)2](OTf)2 (OTf = Trifluorometha- nesulfonate) [11], with Phen and subsequent isolation as a triflate salt. Various spectroscopic data suggested that the obtained complex is identical to the reported one [2]. Figure 2 shows the molecular structure of the title compound. The Ru(II) ion is six-coordinated by four nitrogen donors of two Phen molecules and two carbon atoms of two CO ligands. As expected, two CO ligands lie in the cis position. In the crystal, one of the two triflate ions (OTf−) is partially replaced by a PF6 anion, which is added to promote crystallization. Hence, the total ratio of counterions was confirmed to be OTf−: PF6− = 7:1 in the unit cell. Bond parameters of the primary coordination sphere in this complex cation agree with those of the related [Ru(Bpy)2(CO)2]2+ and [Ru(Phen)2(CH3CN)2]2+ complexes (CSD refcodes: SUKCEG and MUGREL, respectively) [4,15]. Two Ru–CO bond lengths have the same values (1.905(2) and 1.902(2) Å), whereas Ru–N bond lengths trans to CO ligands (2.1100(16) and 2.1135(16) Å) are longer than those trans to Phen-nitrogens (2.0780(16) and 2.0864(16) Å), because of the trans influence of the CO ligands (Table 2). The C–O bond lengths appear to be the same (1.127(2) and 1.126(2) Å), being typical C≡O triple bonds. It is noted that these CO bond lengths are distinctly shorter than those of the isostructural rhenium(I) complex (CSD refcode: RECFAH) [16]. The N1–Ru1– N2 and N3–Ru1–N4 bond angles formed by Phen are less than 90° (79.46(6) and 79.49(6)°), as required by the bite angle of the chelating ligand, Phen. Takase and Oyama / European Journal of Chemistry 12 (4) (2021) 389-393 391 2021 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.12.4.389-393.2151 Table 2. Selected experimental and optimized bond parameters (Å, °) of the title complex cation. Bond lengths Experimental Calculated Bond angles Experimental Calculated Ru1-N1 2.1100(16) 2.158 N1-Ru1-C1 173.82(7) 175.11 Ru1-N2 2.0780(16) 2.135 N3-Ru1-C2 177.16(7) 175.12 Ru1-N3 2.1135(16) 2.158 N2-Ru1-N4 167.98(6) 169.24 Ru1-N4 2.0864(16) 2.135 Ru1-C1-O1 173.36(18) 179.21 Ru1-C1 1.905(2) 1.930 Ru1-C2-O2 174.25(18) 179.24 Ru1-C2 1.902(2) 1.930 C1-Ru1-C2 85.69(8) 91.88 C1-O1 1.127(2) 1.144 N1-Ru1-N2 79.46(6) 78.35 C2-O2 1.126(2) 1.144 N3-Ru1-N4 79.49(6) 78.35 Table 3. Hydrogen-bond geometry (Å, °). D-H…A D-H H…A D…A D-H…A C3-H1…F5i 0.95 2.36 3.112(3) 136 C3-H1…F8i 0.95 2.46 3.096(6) 124 C4-H2…O8i 0.95 2.34 3.188(8) 148 C5-H3…O3ii 0.95 2.45 3.400(3) 174 C8-H4…O5ii 0.95 2.51 3.421(3) 161 C9-H5…O1ii 0.95 2.54 3.014(3) 111 C9-H5…O7iii 0.95 2.39 3.247(8) 150 C9-H5…F11iii 0.95 2.40 3.23(2) 145 C12-H6…O7iii 0.95 2.57 3.373(9) 142 C12-H6…F9iii 0.95 2.54 3.407(7) 152 C12-H6…F11iii 0.95 2.38 3.21(2) 145 C15-H9…O8 0.95 2.50 3.114(8) 122 C15-H9…F12 0.95 2.50 3.148(18) 126 C20-H12…O3iv 0.95 2.57 3.479(3) 161 C24-H14…F9v 0.95 2.50 3.416(7) 161 C26-H16…O4 0.95 2.50 3.310(3) 143 (i) 1-x, y, 1-z. (ii) -x, -y, 1-z. (iii) -x, y, 1-z. (iv) x, y, -1+z. (v) 1+x, y, z. Figure 2. The structures of the molecular components in the title salt ([Ru(Phen)2(CO)2](CF3SO3)1.72(PF6)0.28), with atom labels and displacement ellipsoids for non-H atoms drawn at the 50% probability level. Minor components (PF6−) are shown as light-colored plots. Figure 3. Intermolecular hydrogen bonds (blue) and π−π interactions (green), shown as dashed lines in the crystal packing of the title compound. Ring centroids are shown as colored spheres. The axial groupings are less than 180°, ranging from 167.98(6) to 177.16(7)°. These bond parameters support a distorted octahedral geometry. The Ru–C–O bond angles are also distorted from a linear system (173.36(18) and 174.25(18)°). Additionally, the dihedral angle between the COs are lower than 90° (85.69(8)°), which is consistent with those in [Ru(Bpy)2(CO)2]2+ (88.8(4)°) and [Re(Phen)2(CO)2]+ (86.9(6)°) [4,16]. Intermolecular interactions of the title compound are shown in Figure 3. Several complicated hydrogen bonds are present between the hydrogen atoms of Phen in the complex cation and the adjacent counterions (Table 3). 392 Takase and Oyama / European Journal of Chemistry 12 (4) (2021) 389-393 2021 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.12.4.389-393.2151 Table 4. Comparison between the experimental and the DFT-calculated IR peaks for νCO. Parameters Experimental a Calculated νas(C≡O) (cm-1) 2033 2113 νs(C≡O) (cm-1) 2093 2164 Is/Ias b 1.08 1.01 θ (°) c 87.8 89.8 a KBr method. b Relative absorption intensity. c The value derived from Equation (1). In addition, π−π stacking (3.512(1) Å) is present between adjacent phenyl rings of Phen. These interactions stabilize the crystal packing. 3.2. Comparison of experimental and calculated data The optimized structure of the complex cation was calculated using DFT. Table 2 summarizes the selected bond parameters of both the optimized and the observed structures. The calculated and the experimental values are consistent with each other, and the simulation data also suggest the existence of the trans influence on the carbonyl group. Table 4 shows the result of the vibrational analyses for the CO stretching vibration and the observed IR spectral data. Both data indicate two peaks because of the CO stretching mode in cases of cis configuration. In mononuclear metal complexes having two CO ligands, the bond angle (θ) between the CO ligands can be calculated from the relative intensity (Is/Ias) of the two IR absorptions using Equation 1 [17]: Is/Ias = cotan2(θ/2) (1) The calculated bond angle is 87.8° when the intensity ratio of 1.08 is used from the IR spectrum. This value agrees well with the observed data (85.69(8)°) in Table 2. The intensity ratio (1.01) obtained from computational chemistry also contributed to a similar bond angle (89.8°). Both results support the fact that the two CO ligands are coordinated to the ruthenium(II) ion in the cis configuration. 4. Conclusion In summary, this study demonstrated comparison of the spectroscopic data for [Ru(Phen)2(CO)2]2+ to the values calculated using DFT, as well as the structural characterization of the title compound. Because structural and spectroscopic measurements of the complex provide fundamental data for understanding various properties, this work could contribute to further research in this area. For example, the isostructural Re(I) complex ([Re(Phen)2(CO)2]+) has been studied for practical use as photosensitizers [16]. This suggests that similar applications are available for the present Ru(II) complex. Acknowledgements The authors are indebted to Mr. Takayuki Hoshi of Fukushima University for his experimental assistance. Supporting information CCDC-2073803 contains the supplementary crystallo- graphic data for this paper. These data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/, or by e- mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033. Disclosure statement Conflict of interests: The authors declare that they have no conflict of interest. Ethical approval: All ethical guidelines have been adhered. Sample availability: Samples of the compounds are available from the author. CRediT authorship contribution statement Conceptualization: Dai Oyama; Methodology: Tsugiko Takase, Dai Oyama; Validation: Dai Oyama; Formal Analysis: Tsugiko Takase; Investigation: Tsugiko Takase; Data Curation: Dai Oyama; Writing - Original Draft: Tsugiko Takase, Dai Oyama; Writing - Review and Editing: Dai Oyama; Visualization: Tsugiko Takase; Funding acquisition: Dai Oyama; Supervision: Dai Oyama; Project Administration: Dai Oyama. Funding Japan Society for the Promotion of Science http://dx.doi.org/10.13039/501100001691 ORCID Tsugiko Takase https://orcid.org/0000-0001-6508-4733 Dai Oyama https://orcid.org/0000-0003-2388-9212 References [1]. Bencini, A.; Lippolis, V. Coord. Chem. Rev. 2010, 254 (17–18), 2096– 2180. [2]. Ishida, H.; Fujiki, K.; Ohba, T.; Ohkubo, K.; Tanaka, K.; Terada, T.; Tanaka, T. J. Chem. 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Copyright © 2021 by Authors. This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at http://www.eurjchem.com/index.php/eurjchem/pages/view/terms and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License (http://creativecommons.org/licenses/by-nc/4.0). By accessing the work, you hereby accept the Terms. This is an open access article distributed under the terms and conditions of the CC BY NC License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited without any further permission from Atlanta Publishing House LLC (European Journal of Chemistry). No use, distribution or reproduction is permitted which does not comply with these terms. Permissions for commercial use of this work beyond the scope of the License (http://www.eurjchem.com/index.php/eurjchem/pages/view/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry). http://www.eurjchem.com/index.php/eurjchem/pages/view/terms http://creativecommons.org/licenses/by-nc/4.0 http://www.eurjchem.com/index.php/eurjchem/pages/view/terms 1. Introduction 2. Experimental 2.1. Measurements 2.2. Synthesis of the complex 2.3. Crystallography 3. Results and discussion 3.1. Crystallization and structure 3.2. Comparison of experimental and calculated data 4. Conclusion Acknowledgements Supporting information Disclosure statement Funding ORCID References PrintField10: PrintField11: PrintField12: PrintField13: PrintField14: PrintField20: PrintField21: PrintField22: PrintField23: PrintField24: