A Co 2 N 2 Diamond‐Core Resting State of Cobalt( I ): A Three‐Coordinate Co I Synthon Invoking an Unusual Pincer‐Type Rearrangement
2006; Wiley; Volume: 118; Issue: 20 Linguagem: Inglês
10.1002/ange.200504343
ISSN1521-3757
AutoresAlison R. Fout, Falguni Basuli, Hongjun Fan, John Tomaszewski, John C. Huffman, Mu‐Hyun Baik, Daniel J. Mindiola,
Tópico(s)Catalytic Cross-Coupling Reactions
ResumoAngewandte ChemieVolume 118, Issue 20 p. 3369-3373 Zuschrift A Co2N2 Diamond-Core Resting State of Cobalt(I): A Three-Coordinate CoI Synthon Invoking an Unusual Pincer-Type Rearrangement† Alison R. Fout, Alison R. Fout Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorFalguni Basuli Dr., Falguni Basuli Dr. Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorHongjun Fan Dr., Hongjun Fan Dr. Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorJohn Tomaszewski Dr., John Tomaszewski Dr. Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorJohn C. Huffman Dr., John C. Huffman Dr. Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorMu-Hyun Baik Prof. Dr., Mu-Hyun Baik Prof. Dr. Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorDaniel J. Mindiola Prof. Dr., Daniel J. Mindiola Prof. Dr. [email protected] Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this author Alison R. Fout, Alison R. Fout Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorFalguni Basuli Dr., Falguni Basuli Dr. Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorHongjun Fan Dr., Hongjun Fan Dr. Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorJohn Tomaszewski Dr., John Tomaszewski Dr. Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorJohn C. Huffman Dr., John C. Huffman Dr. Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorMu-Hyun Baik Prof. Dr., Mu-Hyun Baik Prof. Dr. Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this authorDaniel J. Mindiola Prof. Dr., Daniel J. Mindiola Prof. Dr. [email protected] Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA, Fax: (+1) 812-855-8300Search for more papers by this author First published: 05 May 2006 https://doi.org/10.1002/ange.200504343Citations: 23 † This work was supported by Indiana University, the Camille and Henry Dreyfus Foundation (Teacher-Scholar Award to D.J.M.), the Alfred P. Sloan Foundation (Fellowship award to D.J.M.), the National Institutes of Health (HG003894 to M.-H.B.), and the National Science Foundation (CHE-0348941 grant and PECASE award to D.J.M.). A.R.F. acknowledges the Department of Education for a GAANN Fellowship and Dr. Allen R. Siedle for insightful advice. We are also grateful to Prof. Karsten Meyer and Dr. Ingrid Castro-Rodriguez for collecting SQUID data of compound 1. Read the full textAboutPDF ToolsRequest permissionAdd to favorites 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 Die Wahrheit enthüllt: Das Dimer [{(μ2-PNP)Co}2] enthält einen rautenförmigen Co2N2-Kern und verbrückende PNP-Liganden (Bild: Co hellblau, N dunkelblau, P grün, C grau, nur ein C-Atom der Isopropylgruppen ist gezeigt; PNP=[N{2-P(CHMe2)2-4-MeC6H3}2]−). Bei der Reaktion mit ClCPh3, CO oder N2 werden die PNP-Liganden zu terminal chelatisierenden Liganden, wobei vierfach koordinierte Co-Komplexe wie [{(PNP)Co}2(μ2-N2)] entstehen. Supporting Information Supporting information for this article (including experimental details and crystallographic data) is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2006/z504343_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. 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Meli, M. Peruzzini, F. Zanobini, J. Am. Chem. Soc. 1988, 110, 8725–8726. 10.1021/ja00234a041 CASWeb of Science®Google Scholar 9Crystallographic details for 1⋅C7H8: A dark crystal of approximate dimensions 0.15×0.08×0.06 mm3 was selected and mounted on a glass fiber. A total of 3711 reflections (−13≤h≤14, −12≤k≤12, −18≤l≤11) were collected at T=126(2) K in the range of 2.54 to 26.68° of which 2335 were unique (Rint=0.0746); MoKα radiation (λ=0.71073 Å). A direct-methods solution was calculated which provided most non-hydrogen atoms from the E-map. A severely disordered toluene molecule was present in the asymmetric unit. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms not associated with the solvent were located in subsequent Fourier maps and included as isotropic contributors in the final cycles of refinement. No attempt was made to locate the hydrogen atoms on the toluene molecule. 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A total of 13 329 reflections (−17≤h≤17, −21≤k≤20, −21≤l≤20) were collected at T=120(2) K in the range of 2.42 to 24.60o of which 8607 were unique (Rint=0.0594); MoKα radiation (λ=0.71073 Å). A direct-methods solution was calculated which provided most non-hydrogen atoms from the E-map. All non-hydrogen atoms were refined with anisotropic displacement parameters. An Et2O molecule was present in the cell. All hydrogen atoms with the exception of those associated with the solvent were located in subsequent Fourier maps and included as isotropic contributors in the final cycles of refinement. Hydrogen atoms on the Et2O molecule were placed in ideal positions and refined as riding atoms with relative isotropic displacement parameters. The residual peak and hole electron densities were 0.637 and −0.432 e A−3. The absorption coefficient was 0.721 mm−1. The least-squares refinement converged normally with residuals of R(F)=0.0412, wR(F2)=0.0806, and a GOF=0.821 (I>2σ(I)). C56H90Co2N4OP4, triclinic, space group P, a=13.627(1), b=16.380(2), c=16.593(2) Å, α=60.676(2), β=66.601(2), γ=87.963(2)°, V=2904.4(4) Å3, Z=2, ρcalcd=1.232 g cm−3, F(000)=1152. Google Scholar 13The CoCo separation in complex 4 is 2.254(1) Å, a value shorter than reported CoICoI bond lengths. For some CoI dimers containing short CoCo bond lengths, see: Google Scholar 13aS. Stella, C. Floriani, A. Chiesi-Villa, C. Guastini, New J. Chem. 1988, 12, 621–631; CASWeb of Science®Google Scholar 13bJ. J. Schneider, R. Goddard, S. Werner, C. Kruger, Angew. Chem. 1991, 103, 1145–1147; 10.1002/ange.19911030912 CASPubMedWeb of Science®Google ScholarAngew. Chem. Int. Ed. Engl. 1991, 30, 1124–1126. 10.1002/anie.199111241 Web of Science®Google Scholar 14S. Harkins, J. C. Peters, J. Am. Chem. Soc. 2005, 127, 2030–2031. 10.1021/ja043092r CASPubMedWeb of Science®Google Scholar 15Crystallographic details for 5: A green crystal of approximate dimensions 0.30×0.30×0.25 mm3 was selected and mounted on a glass fiber. A total of 3957 reflections (−15≤h≤15, −13≤k≤9, −16≤l≤18) were collected at T=122(2) K in the range of 2.60 to 29.97° of which 3133 were unique (Rint=0.0514); MoKα radiation (λ=0.71073 Å). A direct-methods solution was calculated which provided most non-hydrogen atoms from the E-map. Full-matrix least-squares/difference Fourier cycles were performed to locate the remaining non-hydrogen atoms. All non-hydrogen atoms were refined with anisotropic displacement parameters. The molecule lies on a crystallographic twofold axis. All hydrogen atoms were located in subsequent Fourier maps and included as isotropic contributors in the final cycles of refinement. The residual peak and hole electron densities were 0.555 and −0.332 e A−3. The absorption coefficient was 0.778 mm−1. The leastsquares refinement converged normally with residuals of R(F)=0.0324, wR(F2)=0.0738, and a GOF=0.961 (I>2σ(I)). C28H40CoNO2P2, monoclinic, space group P2/n, a=11.0228(6), b=9.3842(6), c=13.2222(7) Å, β=98.501(2)°, V=1352.7(3) Å3, Z=2, ρcalcd=1.334 g cm−3, F(000)=576. Google Scholar 16Four-coordinate CoI monocarbonyl complexes are scarce (see reference [8k]). Google Scholar 17CCDC-291872–291876 (1–5) 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. Google Scholar Citing Literature Volume118, Issue20May 12, 2006Pages 3369-3373 This is the German version of Angewandte Chemie. Note for articles published since 1962: Do not cite this version alone. Take me to the International Edition version with citable page numbers, DOI, and citation export. We apologize for the inconvenience. 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