Synthesis, structural and spectroscopic characterization of the bis(nitrito-N) octaethylporphyrin cobalt(III) complex

Bader Belhaj Ali, Mohamed Salah Belkhiria, Michel Giorgi, Habib Nasri

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DOI: 10.4236/ojic.2011.13006                

Abstract

The bis(nitrito-N) cobalt(III) octaethylporphyrin derivative with the formula [K(18-C-6)(NO₂)_0.5(H₂O)_0.5]₂ [Co^III(OEP)(NO₂)₂] (1) (OEP = octaethylporphyrin and 18-C-6 is the crown ether18-crown-6) has been synthesized and characterized by UV-vis, IR and proton NMR spectroscopy which indicate, inter alia, that the cobalt ion presents the oxidation state III. The synthesis utilizes 18-crown-6 to solubilize potassium nitrite in the synthetic procedure. This compound crystallizes in the triclinic system, with the centric space group P-1 and the following unit cell parameters: 11.6724(2) Å, b = 12.5715(2) Å, c = 13.4722(3) Å, α = 101.1290(6)°, β = 106.6498(6)°, γ= 109.1507(6)°, Z = 1 and V = 1696.74(5) ų. The crystal structure has been solved and refined to R = 0.0499 and R(w) = 0.1319. The X-rays molecular structure of 1 shows that there is a relatively close interaction of both two NO₂^- axial ligands of the ion complex [Co^III(OEP)(NO₂)₂]^- with the potassium atoms of the two counterions [K(18-C-6) (NO₂)0.5(H₂O)_0.5]^0.5+. The title compound exhibits one-dimension polymer-like structure where “monomers” are linked together through strong O(H₂O)—H…O(nitrito-O) hydrogen bonds.

Keywords

Cobalt(III) Porphyrin; X-Rays Diffraction; UV-Visible; ¹H NMR

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	Nasri, H., Goodwin, J.A. and Scheidt, W.R. (1990) Use of protected binding sites for nitrite binding in iron(III) porphyrinates. Crystal structure of thebis(nitro)(alpha,alpha,alpha,alpha-tetrakis (o-pivalamidophenyl)porphinato)iron(III) anion. Inorganic Chemistry, 29, 185-191. doi:10.1021/ic00327a009
[2]	Nasri, H., Wang, Y., Huynh, B.H., Walker, F.A. and Scheidt, W.R. (1991) Reactions of bis(nitro)(alpha, alpha, alpha, alpha-tetrakis(o-pivalamido phenyl)porphinato) ferrate(III) with pyridine and imidazole. EPR and M?ssbauer spectra and molecular structures of the mixed-ligand species. Inorganic Chemistry, 30, 1483-1489. doi:10.1021/ic00007a012
[3]	Nasri, H., Haller, K.J., Wang, Y., Huynh, B. H., Scheidt, W. R. (1992) Reactions of bis(nitro)[alpha, alpha, alpha, alpha-meso-tetrakis(o-pivalamido phenyl)porphinato]iron (III) with 2,3,5,6-tetrafluorothiophenol and 2,3,5,6-tetrafluorothiophenolate. EPR and M?ssbauer spectra and molecular structures. Inorganic Chemistry, 31, 3459-3467. doi:10.1021/ic00007a012
[4]	Abbreviations used in this paper: Porph; a generalized porphyrin dianion, TPP; dianion of the 5,10,15,20-tetraphenylporphyrin, TpivPP; dianion of ?,?,?,?-terakis(o-pivalamidophenyl) porphyrin (picket fence porphyrin), OEP; dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin, cryptand-222; 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8,8,8]hexacosane, 18-C-6; 1,4,7, 10,13,16-hexaoxacyclooctadecane (18-crown-6), DMAP; 4-(N,N’-dimethylamino) pyridine. 1-MeIm; 1-methylimidazole, 1-2-Me2Im; 1,2-dimethylimidazole,
[5]	Finnegan, M.G., Lappin, A.G. and Scheidt, W.R. (1990) Instability of the nitrite/iron(III) porphyrinate system. Inorganic Chemistry, 29, 181-185. doi:10.1021/ic00327a008
[6]	Nasri, H., Ellison, M.K., Krebs, C., Haynh, B.H. and Scheidt, W.R. (2000) Highly variable π-bonding in the interaction of iron(II) porphyrinates with nitrite. Journal of the American Chemical Society, 122, 10795-10804. doi:10.1021/ja000149a
[7]	Ohba, S. and Seki, H. (2002) Nitro(α,β,γ,δ-tetra phenyl porphyrinato) cobalt(III) benzene solvate. Acta Crystalographica Section E, 58, m162-m164. doi:10.1107/S1600536802005160
[8]	Ohba, S. and Seki, H. (2002) Aqua nitro(α,β,γ,δ-tetra phenylporphyrinato) cobalt(III) di chloro methane solvate. Acta Crystallographica Section E, 58, m169-m171. doi:10.1107/S1600536802005524
[9]	Ohba, S. and Seki, H. (2002) (Ethanol-O) nitro(α,β,γ,δ-tetra phenyl porphyrinato) cobalt(III). Acta Crystallographica Section E, 58, m183-m185. doi:10.1107/S1600536802006049
[10]	Adachi, H., Suzuki, H., Miyazaki, Y., Iimura, Y. and Hoshino, M. (2002) Structure and photochemistry of nitro cobalt(III) tetraphenylporphyrin with axial triphenylphosphine in toluene solutions. Inorganic Chemistry, 41, 2518-2524. doi:10.1021/ic0108686
[11]	Ohba, S., Eishima, M. and Seki, H. (2000) Aqua nitro (α,β,γ,δ-tetraphenylporphyrinato) cobalt(III) N,N-dimethyl form amide disolvate. Acta Crystallographica Section C, 56, e555-e556. doi:10.1021/ic048701a
[12]	Goodw T., Shasho, S., Yongsavanh, M., Echevarria, V., Tiedeken, J., Brown, C., Fromm, G., Lyerly, S., Watson, N., Long, A. and De Nitto, N. (2001) Structural and oxotransfer reactivity differences of hexacoordinate and pentacoordinate (nitro) (tetraphenylporphinato)cobalt(III) derivatives. Inorganic Chemistry, 40, 4217-4225. doi:10.1021/ic001442e
[13]	Goodwin, J., Kurtikyan, T., Standard, J., Walsh, R., Zheng, Bin,Parmley, D., Howard, J., Green, S., Mardyukov, A. and Przybyla, D.E. (2005) Variation of oxo-transfer reactivity of (nitro)cobalt picket fence porphyrin with oxygen-donating ligands. Inorganic Chemistry, 44, 2215-2223. doi:10.1021/ic048701a
[14]	Jene, P.G. and Ibers, J.A. (2000) Structural characterization of the picket fence (TpivPP) porphyrins Co(TpivPP), Co(TpivPP) (NO2)(1-MeIm), and Co(TpivPP)(NO2)(1,2-Me2Im). Inorganic Chemistry, 39, 3823-3827. doi:10.1021/ic000127p
[15]	Ercolani, C., Paoletti, A.M., Pennesi, G. and Rossi, G. (1991) Nitrosyl-nitro redox couples with metal phthalocyanines: Synthesis and characterization of nitro derivatives of cobalt and iron phthalocyanine, dioxygen activation, oxygen-atom transfer and stoichiometric and catalytic oxidetion of terminal olefins. Journal of the Chemical Society, Dalton Trans, 21, 317-321. doi:10.1016/S0020-1693(97)05802-7
[16]	Goodwin, J.A., Coor, J.L., Kavanagh, D.F., Sabbagh, M., Howard, J.W., Adamec, J.R., Parmley, J.D., Tarsis, E.M., Kurtikyan, T.S., Hovhannisyan, A.A., Desrochers, P.J. and Standard, J.M. (2008) Catalytic dioxygen activation by (nitro)(meso-tetrakis(2-N-methylpyridyl)porphyrinato) cobalt(III) cation derivatives electrostatically immobilized in nafion films: An experimental and DFT investigation. Inorganic Chemistry, 47, 7852-7862 doi:10.1021/ic8000762
[17]	Scheidt, W.R. and Tyrkl, I.T. (1994) Crystal and molecular structure of (octaethylporphinato)cobalt(II). Comparison of the structures of four-coordinate M(TPP) and M(OEP) derivatives (M = Fe-Cu). Use of area detector data. Inorganic Chemistry, 33, 1314-1318. doi:10.1021/ic00085a017
[18]	Bolze, F., Drouin, M., Harvey, P.D., Gros, C.P., Espi nosa, E. and Guilard, R. (2003) X-ray structures and lumines-cence properties of Co(II) and Co(III) complexes of cofacial diporphyrins. Journal of Porphyrins and Phthalocyanines, 7, 474-483. doi:10.1142/S1088424603000604
[19]	Otwinowski, Z. and Minor, W. (1997) Processing of X-rays diffraction data collected in oscillation mode. Methods in Enzymology, 276, 307-326.
[20]	Blessing, R.H. (1995) An empirical correction for absorption anisotropy. Acta Crystallographica Section A, 51, 33-38. doi:10.1107/S0108767394005726
[21]	Burla, M.C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G.L., De Caro, L., Giacovazzo, C., Polidori, G. and Spagna, R. (2005) SIR2004: An improved tool for crystal structure determination and refinement. Journal of Applied Crystallography, 38, 381-388. doi:10.1107/S002188980403225X
[22]	McArdle, P. (1995) SORTX—A program for on-screen stick-model editing and autosorting of SHELX files for use on a PC. Journal of Applied Crystallography, 28, 65. doi:10.1107/S0021889894010642
[23]	Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica Section A, 64, 112-122 doi:10.1107/S0108767307043930
[24]	Tail, C.D., Holten, D. and Gouterman, M. (1984) Picosecond photolysis of axial ligands on cobalt(II) and cobalt(III) porphyrins. Journal of the American Chemical Society, 106, 6653-6659. doi:10.1021/ja00334a032
[25]	Belhaj Ali, B. and Nasri, H., Unpublished results.
[26]	Nakamoto, K. (2009) Infrared and Raman spectra of inorganic and coordination compounds, Part B. 6th Edition, John Wiley and Sons, New-Jersey.
[27]	Shirazi, A. and Goff, H.M. (1982) Carbon-13 and proton NMR spectroscopy of four-and five-coordinate cobalt(II) porphyrins: Analysis of NMR isotropic shift. Inorganic Chemistry, 21, 3420-3425. doi:10.1021/ic00139a030
[28]	Cao, Y., Peterson, J. L. and Stolzenberg, A. M. (1998) Metalloradical chemistry of cobalt(II) porphyrins. The syntheses, structure, and reactivity of triphenyltin(II) and trihalomethylcobalt(III) octaethylporphyrin., Inorganic Chemistry, 37, 5173-5179. doi:10.1021/ic980538u
[29]	Konarev, D., Khasanov, S.S., Saito, G., Lybovskaya, R.N., Yoshida, Y. and Otsuka, A. (2003) The interaction of C60, C70, and C60(CN)2 radical anions with cobalt(II) tetraphenylporphyrin in solid multicomponent complexes. Chemistry—A European Journal, 9, 3837-3848. doi:10.1002/chem.200204470
[30]	Ellison, M.K. and Scheidt, W.R. (1998) Asymmetry in nitrosyl metalloporphyrin complexes: The cobalt case. Inorganic Chemistry, 37, 382-383. doi:10.1021/ic971109j
[31]	Summers, J.S., Peterson, J.L. and Stolzenberg, A.M. (1994) Comparison of the structures of the five-coordinate cobalt(II) pyridine, five-coordinate cobalt(III) methyl, and six-coordinate cobalt(III) methyl pyridine complexes of octaethylporphyrin. Journal of the American Chemical Society, 116, 7189-7195. doi:10.1021/ja00095a022
[32]	Belghith, Y. and Nasri, H., Unpublished results.
[33]	Scheidt, W.R. and Reed, C.A. (1981) Spin-state/stere-chemical relationships in iron porphyrins: Implications for the hemoproteins. Chemical Reviews, 81, 543-555. doi:10.1021/cr00046a002
[34]	Iimura, Y., Sakurai, T. and Yamamoto, K. (1988) The crystal and molecular structure of aquachloro (mesotetraphenylporphyrinato)cobalt(III). Bulletin of the Chemical Society of Japan, 61, 821-826. doi:10.1246/bcsj.61.821