Spectroscopic and molecular structure characterization of the bis(2-aminophenol)(5, 10, 15, 20-tetraphenylporphyrinato) cobalt(II) complex


The reaction of the cobalt(II) meso-tetraphenylporphyrin (TPP) starting material with an excess of 2-aminophenol (Hon) in organic solvents, yields the cobalt(II) porphyrin species [CoII(TPP)(Hon)2] (1). This compound has been characterized by UV-vis., IR, MSI MS and 1H NMR spectroscopy. The UV-vis data and especially the proton NMR results, for the isolated product, indicated that complex 1 is a Co(II) mesoporphyrin derivative.The X-ray molecular structure of the title compound bis(2-aminophenol) (tetraphenylporphyrinato) cobalt(II) has been determined. This structure is the first one reported of a metalloporphyrin with a 2-aminophenol axial ligand species. The central metal is hexacoordinated by the four nitrogen atoms of the pyrrole rings and the nitrogen atoms of the two Hon trans axial ligands.

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Belghith, Y. , Mansour, A. , Daran, J. and Nasri, H. (2012) Spectroscopic and molecular structure characterization of the bis(2-aminophenol)(5, 10, 15, 20-tetraphenylporphyrinato) cobalt(II) complex. Open Journal of Inorganic Chemistry, 2, 81-87. doi: 10.4236/ojic.2012.24012.

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The authors declare no conflicts of interest.


[1] Gerber, T.I.A., Luzipo, D. and Mayer, P. (2004) The reaction of the cis-dioxorhenium(V) core with N,O-donor ligands: monoand bidentate coordination of 3-methyl2-aminophenol. Inorganica Chimica Acta , 357, 429-435. HUdoi:10.1016/j.ica.2009.02.037
[2] Hassenein, M., Abdo M., Gerges, S. and El-Khalafy, S. (2008) Study of the oxidation of 2-aminophenol by molecular oxygen catalyzed by cobalt(II) phthalocyaninetetrasodiumsulfonate in water. Journal of Molecular Catalysis A, 287, 53-56. HUdoi:10.1016/j.molcata.2006.11.045UH
[3] Abbreviations used: TPP: dianion of meso-tetraphenylporphyrin; Hon: 2-aminophenol (or ortho-aminophenol); OAc: acetato ; ?2-AT: ?2-3-amino-(S)-tyrosinato; adtpb: (2-amino-4,6-di-t-butylphenol-N); noo’(2,4-di-tbutyl-6) (salicylideneamino) phenolato-N-O-O’; d: opa2aminophenolato-N,O; PhCN: benzonitrile; BAP: tetrabutylammonium perchlorate.
[4] Gao, X.-Y., Xing, L.-X., Chen, Z.-F., Bao, Y.-C., Yang, J.-H., Wu, M.-F., Xiong, R.-G., You, X.-Z. and Fun, H.-K. (2003). Synthesis and crystal structure of a biologically relevant homochiral two-dimensional metal-organic herring-bone molecular grid: Bis(3-amino-(S)-tyrosinato) cobalt(II). Chinese Journal of Inorganic Chemistry, 19, 802.
[5] Alder, A.D., Longo, F.R, Finarelli, J.D., Gildmacher, J., Assour, J. and Korsakoff, L. (1967) A simplified synthesis for mesotetraphenyl porphine. Journal of Organic Chemistry, 32, 476-476. HUdoi:10.1021/jo01288a053UH
[6] Mansour, A., Belkhiria , M.S., Daran, J.C. and Nasri, H. (2010) (5,10,15,20-tetraphenylporphyrinato) cobalt(II)18-crown-6 (1/1). Acta Crystallographica Section E, 66, m509-m510. HUdoi:10.1107/S1600536810012080U
[7] Oxford Diffraction (2009). Chrysalis Promotions, Oxford Diffraction Ltd., Abingdon, Oxfordshire, England. HUdoi:10.1021/ic50166a056U
[8] 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. HUdoi:10.1107/S002188980403225XU
[9] Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica Section E, 64, 112-122. HUdoi.10.1107/S0108767307043930U
[10] Mansour, A. and Nasri, H. (2012) “Synthesis, crystal structure and spectroscopic characterization of 1D Co(II) coordination polymers {[CoII(α,β,α,β-TpivPP)(μ-4,4’-bp y)2]}n and {[CoII(TPP)(μ-4,4’-bpy)2]}n with the (a,b,a,btetrakis(o-pivalamidophenyl)porphyrin) a,b,a,b-TpivPP) and the tetraphenylporphyrin (TPP). In press.
[11] Hoshino, M., Sonoki, H., Miyazaki,Y., Iimura, Y. and Yamamoto, K. (2000) Structure and photo chemistry of dicyanocobalt(III) tetraphenyl porphyrin. Photochromic reaction caused by photodissociation of axial ligand. Inorganic Chem istry, 39, 4850-4857. HUdoi: 10.1021/ic000408xUH
[12] Shirazi, A. and Goff, H.M. (1982) Carbon-13 and proton NMR spectroscopy of fourand five-coordinate cobalt(II) porphyrins: Analysis of NMR isotropic shifts. Inorganic Chemistry, 21, 3420-3425. HUdoi: 10.1021/ic00139a030U
[13] La Mar, G. N. and Walker, F.A. (1973) Proton nuclear magnetic resonance and electron spin resonance investigation of axial solvation in planar, low-spin cobalt(II) porphyrin complexes. Journal of American Chemical Society, 95, 1790-1796. HUdoi:10.1021/ja00787a017U
[14] Choi I-K., Lin, Y., Wei, Z. and Rayan, M.D. (1997) Reactions of hydroxylamine with metal porphyrins. Inorganic Chemistry, 36, 3113-3118. HUdoi:10.1021/ic9605783UH
[15] Farrugia, L.J. (1997) ORTEP-3 for windows a ver sion of ORTEP-III with a graphical user interface (GUI). Journal of Applied Crystallography, 30, 565. HUdoi:10.1107/S0021889897003117U
[16] Allen, F.H. (2002) The Cambridge Structural Data base: A quarter of a million crystal structures and rising. Acta Crystallographica Section B, 58, 380-388. HUdoi:10.1107/S0108768102003890U
[17] Mayer, P., Potgieter, K.C. and Gerber, T.I.A. (2010) Rhenium (I), (III) and (V) complexes of tridentate ONX (X=O, N, S)-donor Schiff bases. Polyhedron, 29, 14231430. HUdoi: 10.1016/j.poly.2010.01.013UH
[18] Gerber, T.I.A., Betz, R., Booysen, I.N., Potgieter, K.C. and Mayer, P. (2011) Coordination of bidentate aniline derivatives to the fac-[Re(CO)3]+ core. Polyhedron, 30, 1739-1745. HUdoi: 10.1016/j.poly.2011.04.019UH
[19] Iimura,Y., Sakurai, T. and Yamamoto, K. ( 1988) The crystal and molecular structure of aquachloro (meso-tetraphenylporphyrinato) cobalt(III). Bulletin of the Chemical Society of Japan, 61, 821-826. HUdoi: 10.1246/bcsj.61.821UH.

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