A meso ‐Spiro[Cyclopentadiene‐Isoporphyrin] from a Phenylethynyl Porphyrin Platinum(II) Pincer Complex
2012; Wiley; Volume: 51; Issue: 13 Linguagem: Inglês
10.1002/anie.201109091
ISSN1521-3773
AutoresS. Anabuki, Hiroshi Shinokubo, Naoki Aratani, Atsuhiro Osuka,
Tópico(s)Oxidative Organic Chemistry Reactions
ResumoAngewandte Chemie International EditionVolume 51, Issue 13 p. 3174-3177 Communication A meso-Spiro[Cyclopentadiene-Isoporphyrin] from a Phenylethynyl Porphyrin Platinum(II) Pincer Complex† Shoma Anabuki, Shoma Anabuki Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)Search for more papers by this authorProf. Dr. Hiroshi Shinokubo, Corresponding Author Prof. Dr. Hiroshi Shinokubo [email protected] Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603 (Japan) Hiroshi Shinokubo, Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603 (Japan) Naoki Aratani, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) Atsuhiro Osuka, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)Search for more papers by this authorDr. Naoki Aratani, Corresponding Author Dr. Naoki Aratani [email protected] Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) PRESTO, Japan Science and Technology Agency (Japan) Hiroshi Shinokubo, Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603 (Japan) Naoki Aratani, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) Atsuhiro Osuka, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)Search for more papers by this authorProf. Dr. Atsuhiro Osuka, Corresponding Author Prof. Dr. Atsuhiro Osuka [email protected] Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) Hiroshi Shinokubo, Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603 (Japan) Naoki Aratani, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) Atsuhiro Osuka, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)Search for more papers by this author Shoma Anabuki, Shoma Anabuki Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)Search for more papers by this authorProf. Dr. Hiroshi Shinokubo, Corresponding Author Prof. Dr. Hiroshi Shinokubo [email protected] Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603 (Japan) Hiroshi Shinokubo, Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603 (Japan) Naoki Aratani, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) Atsuhiro Osuka, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)Search for more papers by this authorDr. Naoki Aratani, Corresponding Author Dr. Naoki Aratani [email protected] Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) PRESTO, Japan Science and Technology Agency (Japan) Hiroshi Shinokubo, Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603 (Japan) Naoki Aratani, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) Atsuhiro Osuka, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)Search for more papers by this authorProf. Dr. Atsuhiro Osuka, Corresponding Author Prof. Dr. Atsuhiro Osuka [email protected] Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) Hiroshi Shinokubo, Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603 (Japan) Naoki Aratani, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan) Atsuhiro Osuka, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)Search for more papers by this author First published: 15 February 2012 https://doi.org/10.1002/anie.201109091Citations: 20 † This work was partly supported by Grants-in-Aid for Scientific Research (Nos. 19205006 (A) and 20108001 "pi-Space") and for Young Scientists (A) from MEXT, and by JST PRESTO program. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract A good catch: The oxidation of a phenylethynyl PtII pincer complex with iodine led to formal reductive elimination but without the liberation of PtII, which was caught by the 2-pyridyl substituents on the NiII porphyrin. The unique reactivity of the PtII pincer complex led to the formation of a meso-spiro[cyclopentadiene-isoporphyrin]. Supporting Information Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Filename Description anie_201109091_sm_miscellaneous_information.pdf5.8 MB miscellaneous_information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1 1aM. Albrecht, G. van Koten, Angew. Chem. 2001, 113, 3866; Angew. Chem. Int. Ed. 2001, 40, 3750; 1bJ. Dupont, C. S. Consorti, J. Spencer, Chem. Rev. 2005, 105, 2527; 1cM. E. van der Boom, D. Milstein, Chem. Rev. 2003, 103, 1759; 1dJ. T. Singleton, Tetrahedron 2003, 59, 1837. 2 2aS. Yamaguchi, T. Katoh, H. Shinokubo, A. Osuka, J. Am. Chem. Soc. 2007, 129, 6392; 2bJ. Yamamoto, T. Shimizu, S. Yamaguchi, N. Aratani, H. Shinokubo, A. Osuka, J. Porphyrins Phthalocyanines 2011, 15, 534; 2cJ. Song, N. Aratani, J. H. Heo, D. Kim, H. Shinokubo, A. Osuka, J. Am. Chem. Soc. 2010, 132, 11868. 3For other peripherally PdII- and PtII-metalated porphyrins, see: 3aD. P. Arnold, Y. Sakata, K. Sugiura, E. I. Worthington, Chem. Commun. 1998, 2331; 3bR. D. Hartnell, D. P. Arnold, Eur. J. Inorg. Chem. 2004, 1262; 3cM. J. Hodgson, P. C. Healy, M. L. Williams, D. P. Arnold, J. Chem. Soc. Dalton Trans. 2002, 4497; 3dY. Matano, K. Matsumoto, Y. Nakano, H. Uno, S. Sakaki, H. Imahori, J. Am. Chem. Soc. 2008, 130, 4588; 3eY. Matano, K. Matsumoto, H. Hayashi, Y. Nakao, T. Kumpulainen, V. I. Chukharev, N. V. Tkachenko, H. Lemmetyinen, S. Shimizu, N. Kobayashi, D. Sakamaki, A. Ito, K. Tanaka, H. Imahori, J. Am. Chem. Soc. 2012, 134, 1825. 4 4aS. Yamaguchi, T. Katoh, H. Shinokubo, A. Osuka, J. Am. Chem. Soc. 2008, 130, 14440; 4bS. Yamaguchi, H. Shinokubo, A. Osuka, Inorg. Chem. 2009, 48, 795. 5K. Yoshida, S. 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Porphyrins Phthalocyanines 2011, 15, 918. 10Crystal data for 4: C80H82N6NiPt⋅5 CHCl3, Mr=1973.12, triclinic, space group P (no. 2), a=14.5824(12), b=17.7665(15), c=17.7761(15) Å, α=91.675(2), β=102.2010(10), γ=98.3630(10)°, V=4444.9(6) Å3, Z=2, T=90(2) K, Dcalcd=1.474 g cm−3, R1=0.0503 (I>2σ(I)), Rw=0.1384 (all data), GOF=1.055; 5: C80H83N6ONiPtI, Mr=1525.22, monoclinic, space group P2/n (no. 13), a=13.0267(4), b=21.2118(7), c=35.4248(11) Å, β=97.8789(12)°, V=9696.2(5) Å3, Z=4, T=93(2) K, Dcalcd=1.045 g cm−3, R1=0.0858 (I>2σ(I)), Rw=0.2397 (all data), GOF=0.833; 6: C80H82N6NiPtI2, Mr=1635.12, triclinic, space group P (no. 2), a=11.7306(2), b=14.8418(4), c=26.9882(5) Å, α=99.1516(10), β=98.6274(14), γ=111.7004(9)°, V=4197.00(15) Å3, Z=2, T=93(2) K, Dcalcd=1.294 g cm−3, R1=0.0969 (I>2σ(I)), Rw=0.2611 (all data), GOF=1.007; 9: C88H87N6Ni1Pt1I5⋅2.73 CHCl3⋅0.27 I2, Mr=2511.35, triclinic, space group P (no. 2), a=15.2725(3), b=17.3994(3), c=19.6955(4) Å, α=88.3329(7), β=69.6501(7), γ=74.1108(7)°, V=4706.89(16) Å3, Z=2, T=93(2) K, Dcalcd=1.772 g cm−3, R1=0.0973 (I> 2σ(I)), Rw=0.2465 (all data), GOF=1.027. The contributions to the scattering arising from the presence of the disordered solvents in the crystals of 5 and 6 were removed by use of the utility SQUEEZE in the PLATON software package.[14] CCDC 857634 (4), 857635 (5), 857636 (6), and 857637 (9) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. 11G. van Koten, J. Terheiden, J. A. M. van Beek, I. C. M. Wehman-Ooyevaar, F. Muller, C. H. Stam, Organometallics 1990, 9, 903. 12An alternative route involving the initial coordination-insertion of iodoethynylbenzene between the porphyrin–PtII bond followed by reductive elimination also provides 12. However, this route may be considered energetically unfavorable because of the rigid structure of the porphyrin pincer part. 13 13aR. D. Hartnell, A. J. Edwards, D. P. Arnold, J. Porphyrins Phthalocyanines 2002, 6, 695; 13bD. P. Arnold, P. C. Healy, M. J. Hodgson, M. L. Williams, J. Organomet. Chem. 2000, 607, 41. 14Squeeze-Platon: 14aA. L. Spek, PLATON, A Multipurpose Crystallographic Tool, Utrecht, The Netherlands, 2005; 14bP. van der Sluis, A. L. Spek, Acta Crystallogr. Sect. A 1990, 46, 194. Citing Literature Volume51, Issue13March 26, 2012Pages 3174-3177 ReferencesRelatedInformation
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