Voltar
Artigo Acesso aberto Revisado por pares
BIBTEX RIS

Five‐Membered Metallacyclic Allenoids: Synthesis and Structure of Remarkably Stable Strongly Distorted Cyclic Allene Derivatives

2008; Wiley; Volume: 47; Issue: 14 Linguagem: Inglês

10.1002/anie.200705615

ISSN

1521-3773

Autores

Juri Ugolotti, G. Dierker, Gerald Kehr, Roland Fröhlich, Stefan Grimme, Gerhard Erker,

Tópico(s)

Organometallic Complex Synthesis and Catalysis

Resumo

Angewandte Chemie International EditionVolume 47, Issue 14 p. 2622-2625 Communication Five-Membered Metallacyclic Allenoids: Synthesis and Structure of Remarkably Stable Strongly Distorted Cyclic Allene Derivatives† Juri Ugolotti Dr., Juri Ugolotti Dr. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this authorGereon Dierker Dr., Gereon Dierker Dr. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this authorGerald Kehr Dr., Gerald Kehr Dr. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this authorRoland Fröhlich Dr., Roland Fröhlich Dr. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this authorStefan Grimme Prof. Dr., Stefan Grimme Prof. Dr. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this authorGerhard Erker Prof. Dr., Gerhard Erker Prof. Dr. [email protected] Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this author Juri Ugolotti Dr., Juri Ugolotti Dr. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this authorGereon Dierker Dr., Gereon Dierker Dr. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this authorGerald Kehr Dr., Gerald Kehr Dr. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this authorRoland Fröhlich Dr., Roland Fröhlich Dr. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this authorStefan Grimme Prof. Dr., Stefan Grimme Prof. Dr. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this authorGerhard Erker Prof. Dr., Gerhard Erker Prof. Dr. [email protected] Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-833-6503Search for more papers by this author First published: 18 March 2008 https://doi.org/10.1002/anie.200705615Citations: 79 † Financial support from the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie is gratefully acknowledged. 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 Metallocene lends a hand: Treatment of [bis(alkynyl)HfCp2] complexes with HB(C6F5)2 results in 1,1-hydroboration and subsequent carbon–carbon coupling to yield the corresponding metallacyclopenta-1,2-diene derivatives (see structure of the trimethylsilyl derivative; Hf brown, B red, Si blue, F green, C black). X-ray diffraction and a quantum chemical analysis reveal an electronic structure between a bent cyclic allene and a coordinated butenyne. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z705615_s.pdf or from the author. 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 1M. Christl in Modern Alkene Chemistry (Eds.: ), Wiley-VCH, Weinheim, 2004, pp. 243–357, and references therein. 2For rare cases of the observation of matrix-isolated six-membered heterocyclic allenes, see, for example: 2aA. F. Nikitina, R. S. Sheridan, Org. Lett. 2005, 7, 4467–4470; 2bT. Khasanova, R. S. Sheridan, J. Am. Chem. Soc. 2000, 122, 8585–8586. 3Six-membered allenes that contain several heavy heteroatoms and thus exhibit much larger perimeters can be very stable. See, for example: 3aM. A. Hofmann, U. Bergsträßer, G. J. Reiß, L. Nyulászi, M. Regitz, Angew. Chem. 2000, 112, 1318–1320; Angew. Chem. Int. Ed. 2000, 39, 1261–1263; 3bF. Hojo, W. Ando, Synlett 1995, 880–890; 3cY. Pang, S. A. Petrich, V. G. Young, Jr., M. S. Gordon, T. J. Barton, J. Am. Chem. Soc. 1993, 115, 2534–2537; 3dT. Shimizu, F. Hojo, W. Ando, J. Am. Chem. Soc. 1993, 115, 3111–3115. 4 4aK. J. Daoust, S. M. Hernandez, K. M. Konrad, I. D. Mackie, J. Winstanley, Jr., R. P. Johnson, J. Org. Chem. 2006, 71, 5708–5714; 4bR. O. Angus, Jr., M. W. Schmidt, R. P. Johnson, J. Am. Chem. Soc. 1985, 107, 532–537. 5 5aB. Engels, J. C. Schöneboom, A. F. Münster, S. Groetsch, M. Christl, J. Am. Chem. Soc. 2002, 124, 287–297. See also: 5bM. Christl, M. Braun, H. Fischer, S. Groetsch, G. Müller, D. Leusser, S. Deuerlein, D. Stalke, M. Arnone, B. Engels, Eur. J. Org. Chem. 2006, 5045–5058. 6 6aU. Rosenthal, A. Ohff, W. Baumann, R. Kempe, A. Tillack, V. V. Burlakov, Angew. Chem. 1994, 106, 1678–1680; Angew. Chem. Int. Ed. Engl. 1994, 33, 1605–1607. Review: 6bU. Rosenthal, V. V. Burlakov, P. Arndt, W. Baumann, A. Spannenberg, Organometallics 2005, 24, 456–471. 7 7aN. Suzuki, N. Aihara, H. Takahara, T. Watanabe, M. Iwasaki, M. Saburi, D. Hashizume, T. Chihara, J. Am. Chem. Soc. 2004, 126, 60–61; 7bN. Suzuki, M. Nishiura, Y. Wakatsuki, Science 2002, 295, 660–663. See also: 7cU. Rosenthal, Angew. Chem. 2004, 116, 3972–3977; Angew. Chem. Int. Ed. 2004, 43, 3882–3887; 7dK. C. Lam, Z. Lin, Organometallics 2003, 22, 3466–3470; 7eE. D. Jemmis, A. K. Phukan, H. Jiao, U. Rosenthal, Organometallics 2003, 22, 4958–4965. 8 8aR. E. von H. Spence, W. E. Piers, Y. Sun, M. Parveez, L. R. MacGillivray, M. J. Zaworotko, Organometallics 1998, 17, 2459–2469; 8bD. J. Parks, W. E. Piers, G. P. A. Yap, Organometallics 1998, 17, 5492–5503; 8cW. Piers, T. Chivers, Chem. Soc. Rev. 1997, 26, 345–354; 8dD. J. Parks, R. E. von H. Spence, W. E. Piers, Angew. Chem. 1995, 107, 895–897; Angew. Chem. Int. Ed. Engl. 1995, 34, 809–811; 8eR. E. von H. Spence, D. J. Parks, W. E. Piers, M.-A. MacDonald, M. J. Zaworotko, S. J. Rettig, Angew. Chem. 1995, 107, 1337–1340; Angew. Chem. Int. Ed. Engl. 1995, 34, 1230–1233. 9 9aB. Wrackmeyer, G. Kehr, A. Sebald, J. Kümmerlen, Chem. Ber. 1992, 125, 1597–1603; 9bB. Wrackmeyer, G. Kehr, R. Boese, Angew. Chem. 1991, 103, 1374–1376; Angew. Chem. Int. Ed. Engl. 1991, 30, 1370–1372. Reviews: 9cB. Wrackmeyer in Advances in Boron Chemistry (Ed.: ), Royal Society of Chemistry, Cambridge, 1997, pp. 73–83; 9dB. Wrackmeyer, Coord. Chem. Rev. 1995, 145, 125–156. 10X-ray crystal structure analysis for 5 a: C32H29BF10HfSi2, M=849.03, yellow-orange crystal 0.50×0.15×0.07 mm, monoclinic, space group P21/c (No. 14), a=19.4148(2), b=9.8658(1), c=18.8991(2) Å, β=115.591(1)°, V=3264.86(6) Å3, Z=4, ρcalcd=1.727 g cm−3, μ=3.348 mm−1, empirical absorption correction (0.285≤T≤0.799), λ=0.71073 Å, T=223 K, ω and ϕ scans, 20 262 reflections collected (±h, ±k, ±l), [(sinθ)/λ]=0.67 Å−1, 8106 independent (Rint=0.033) and 6979 observed reflections [I≥2σ(I)], 422 refined parameters, R=0.031, wR2=0.076, max (min) residual electron density 0.85 (−1.18) e Å−3, hydrogen atoms calculated and refined as riding atoms. X-ray crystal structure analysis for 5 b: C34H29BF10Hf, M=816.87, orange crystal 0.35×0.30×0.10 mm, triclinic, space group P (No. 2), a=9.619(1), b=18.416(1), c=18.506(1) Å, α=79.43(1), β=76.80(1), γ=80.25(1)°, V=3109.5(4) Å3, Z=4, ρcalcd=1.745 g cm−3, μ=3.439 mm−1, empirical absorption correction (0.379≤T≤0.725), λ=0.71073 Å, T=198 K, ω and ϕ scans, 33 651 reflections collected (±h, ±k, ±l), [(sinθ)/λ]=0.67 Å−1, 15 092 independent (Rint=0.046) and 11 114 observed reflections [I≥2σ(I)], 841 refined parameters, R=0.045, wR2=0.100, max (min) residual electron density 2.11 (−2.98) e Å−3, two almost identical molecules in the asymmetric unit, hydrogen atoms calculated and refined as riding atoms. Data sets were collected with Nonius KappaCCD diffractometer equipped with a rotating anode generator. Programs used: data collection COLLECT (Nonius B.V., 1998), data reduction Denzo-SMN (Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307–326), absorption correction Denzo ( Z. Otwinowski, D. Borek, W. Majewski, W. Minor, Acta Crystallogr. Sect. A 2003, 59, 228–234), structure solution SHELXS-97 ( G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467–473), structure refinement SHELXL-97 ( G. M. Sheldrick, Universität Göttingen, 1997), graphics SCHAKAL ( E. Keller, Universität Freiburg, 1997). CCDC-664142 (5 b) and 664143 (5 a) 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. 11See the bonding features of [(s-cis-η4-butadiene)zirconocene] for comparison: 11aG. Erker, G. Kehr, R. Fröhlich, Adv. Organomet. Chem. 2004, 51, 109–162; 11bG. Erker, G. Kehr, R. Fröhlich, J. Organomet. Chem. 2004, 689, 4305–4318; 11cG. Erker, C. Krüger, G. Müller, Adv. Organomet. Chem. 1985, 24, 1–39; 11dG. Erker, K. Engel, U. Korek, P. Czisch, H. Berke, P. Caubère, P. Vanderesse, Organometallics 1985, 4, 1531–1536; 11eG. Erker, K. Engel, C. Krüger, G. Müller, Organometallics 1984, 3, 128–133. 12All DFT results refer to fully optimized structures using the non-empirical PBE density functional with corrections for intramolecular dispersion effects (PBE-D) and employing large triple-zeta (TZVPP′) AO basis sets. For details and references, see the Supporting Information. 13For examples for remotely related structures, see: 13aV. V. Burlakov, P. Arndt, W. Baumann, A. Spannenberg, U. Rosenthal, Organometallics 2004, 23, 5188–5192; 13bS. Bredeau, G. Delmas, N. Pirio, P. Richard, B. Donnadieu, P. Meunier, Organometallics 2000, 19, 4463–4467; 13cP. Štepnička, R. Gyepes, I. Císřová, M. Horáček, J. Kubišta, K. Mach, Organometallics 1999, 18, 4869–4880; 13dD. P. Hsu, W. M. Davis, S. L. Buchwald, J. Am. Chem. Soc. 1993, 115, 10394–10395; 13eP. W. Blosser, J. C. Gallucci, A. Wojcicki, J. Am. Chem. Soc. 1993, 115, 2994–2995. Citing Literature Volume47, Issue14March 25, 2008Pages 2622-2625 ReferencesRelatedInformation

Referência(s)