Reversible Intramolecular Coupling of the Terminal Borylene and a Carbonyl Ligand of [Cp(CO)2MnBtBu]†
Corresponding Author
Prof. Dr. Holger Braunschweig
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)Search for more papers by this authorDr. Krzysztof Radacki
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)
Search for more papers by this authorDr. Rong Shang
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)
Search for more papers by this authorDr. Christopher W. Tate
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Holger Braunschweig
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)Search for more papers by this authorDr. Krzysztof Radacki
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)
Search for more papers by this authorDr. Rong Shang
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)
Search for more papers by this authorDr. Christopher W. Tate
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)
Search for more papers by this authorWe are grateful to the European Research Council (Advanced Investigator Grant to H.B.) for financial support.
Graphical Abstract
Cyclic complex 2 with bridging carbonyl ligands was synthesized from a facile and reversible intermolecular carbonyl–borylene ligand coupling reaction at room temperature. Complex 2 exhibits an unprecedented coordination mode for boron–metal complexes, which is also reflected in its remarkable 11B NMR chemical shift of −57.2 ppm. Findings from spectroscopic, X-ray, and computational studies are presented, along with a proposed mechanism.
Supporting Information
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References
- 1
- 1aL. M. Caldwell, Adv. Organomet. Chem. 2008, 56, 1–94;
- 1bT. D. McGrath, F. G. A. Stone, Adv. Organomet. Chem. 2005, 53, 1–40;
- 1cM. I. Bruce, P. J. Low, Adv. Organomet. Chem. 2004, 50, 179–444;
- 1dP. J. Brothers, Adv. Organomet. Chem. 2000, 46, 223–321;
- 1eS. A. Brew, F. G. A. Stone, Adv. Organomet. Chem. 1993, 35, 135–186;
- 1fA. Mayr, H. Hoffmeister, Adv. Organomet. Chem. 1991, 32, 227–324;
- 1gF. G. A. Stone, Adv. Organomet. Chem. 1990, 31, 53–89;
- 1hW. E. Buhro, M. H. Chisholm, Adv. Organomet. Chem. 1987, 27, 311–369;
- 1iH. P. Kim, R. J. Angelici, Adv. Organomet. Chem. 1987, 27, 51–111;
- 1jM. A. Gallop, W. R. Roper, Adv. Organomet. Chem. 1986, 25, 121–198;
- 1kE. O. Fischer, Adv. Organomet. Chem. 1976, 14, 1–32.
- 2See the Supporting Information for computational details.
- 3
- 3aR. Choukroun, C. Lorber, C. Lepetit, B. Donnadieu, Organometallics 2003, 22, 1995–1997;
- 3bR. R. Schrock, C. Czekelius, Adv. Synth. Catal. 2007, 349, 55–77;
- 3cR. H. Grubbs, T. M. Trnka, Ruthenium Org. Synth. 2004, 153–177;
- 3dR. H. Grubbs, D. M. Lynn, Aqueous-Phase Organomet. Catal., 2nd ed., 2004, 550–566;
- 3eR. H. Grubbs, T. M. Trnka, M. S. Sanford, Curr. Methods Inorg. Chem. 2003, 3, 187–231;
- 3fB. C. Gates, Angew. Chem. 1993, 105, 240–241; Angew. Chem. Int. Ed. Engl. 1993, 32, 228–229;
- 3gT. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18–29;
- 3hR. R. Schrock, Acc. Chem. Res. 1986, 19, 342–348;
- 3iP. Jean-Louis Hérisson, Y. Chauvin, Makromol. Chem. 1971, 141, 161–176.
10.1002/macp.1971.021410112 Google Scholar
- 4
- 4aX. Wu, M. Tamm, Beilstein J. Org. Chem. 2011, 7, 82–93;
- 4bJ. M. Blackwell, J. S. Figueroa, F. H. Stephens, C. C. Cummins, Organometallics 2003, 22, 3351–3353.
- 5
- 5aF. R. Kreissl, K. Eberl, W. Üdelhoven, Chem. Ber. 1977, 110, 3782–3791;
- 5bW. J. Sieber, D. Neugebauer, F. R. Kreissl, Z. Naturforsch. B 1985, 40, 1500–1503;
- 5cW. J. Sieber, K. Eberl, M. Wolfgruber, F. R. Kreissl, Z. Naturforsch. B 1983, 38, 1159–1160;
- 5dF. R. Kreissl, H. Keller, W. Schütt, J. Organomet. Chem. 1992, 441, 75–80.
- 6
- 6aA. C. Filippou, Org. Synth. Organomet. Proc. Symp. 5th 1997, 97–119;
- 6bA. C. Filippou, D. Wossner, G. Kociok-Kohn, I. Hinz, J. Organomet. Chem. 1997, 541, 333–343;
- 6cA. F. Hill, J. M. Malget, A. J. P. White, D. J. Williams, Chem. Commun. 1996, 721–722;
- 6dE. O. Fischer, C. Apostolidis, E. Dornberger, A. C. Filippou, B. Kanellakopulos, B. Lungwitz, J. Müller, B. Powietzka, J. Rebizant, W. Roth, Z. Naturforsch. B 1995, 50, 1382–1395;
- 6eT.-Y. Lee, A. Mayr, J. Am. Chem. Soc. 1994, 116, 10300–10301;
- 6fA. Mayr, R. T. Chang, T.-Y. Lee, O. K. Cheung, M. A. Kjelsberg, G. A. McDermott, E. D. Van, J. Organomet. Chem. 1994, 479, 47–53;
- 6gK. A. Belsky, M. F. Asaro, S. Y. Chen, A. Mayr, Organometallics 1992, 11, 1926–1936;
- 6hA. Mayr, S. M. Holmes, C. M. Bastos, Organometallics 1992, 11, 4358–4362;
- 6iP. K. Baker, G. K. Barker, D. S. Gill, M. Green, A. G. Orpen, I. D. Williams, A. J. Welch, J. Chem. Soc. Dalton Trans. 1989, 1321–1323;
- 6jJ. B. Sheridan, D. B. Pourreau, G. L. Geoffroy, A. L. Rheingold, Organometallics 1988, 7, 289–294;
- 6kH. P. Kim, S. Kim, R. A. Jacobson, R. J. Angelici, Organometallics 1986, 5, 2481–2488;
- 6lJ. B. Sheridan, G. L. Geoffroy, A. L. Rheingold, Organometallics 1986, 5, 1514–1515;
- 6mS. J. Holmes, R. R. Schrock, M. R. Churchill, H. J. Wasserman, Organometallics 1984, 3, 476–484;
- 6nE. O. Fischer, A. C. Filippou, H. G. Alt, K. Ackermann, J. Organomet. Chem. 1983, 254, C 21–C23.
- 7
- 7aI. Baxter, A. F. Hill, J. M. Malget, A. J. P. White, D. J. Williams, Chem. Commun. 1997, 2049–2050;
- 7ba. F. Hill, J. M. Malget, Chem. Commun. 1996, 1177–1178.
- 8H. Braunschweig, T. Wagner, Angew. Chem. 1995, 107, 904–905; Angew. Chem. Int. Ed. Engl. 1995, 34, 825–826.
- 9
- 9aS. Aldridge, D. L. Coombs, Coord. Chem. Rev. 2004, 248, 535–559;
- 9bC. E. Anderson, H. Braunschweig, R. D. Dewhurst, Organometallics 2008, 27, 6381–6389;
- 9cH. Braunschweig, C. Kollann, F. Seeler, Struct. Bonding (Berlin) 2008, 130, 1–27;
- 9dH. Braunschweig, R. D. Dewhurst, A. Schneider, Chem. Rev. 2010, 110, 3924–3957.
- 10H. Braunschweig, M. Burzler, K. Radacki, F. Seeler, Angew. Chem. 2007, 119, 8217–8219; Angew. Chem. Int. Ed. 2007, 46, 8071–8073.
- 11
- 11aD. H. Berry, J. E. Bercaw, A. J. Jircitano, K. B. Mertes, J. Am. Chem. Soc. 1982, 104, 4712–4715;
- 11bE. M. Carnahan, J. D. Protasiewicz, S. J. Lippard, Acc. Chem. Res. 1993, 26, 90–97;
- 11cR. N. Vrtis, S. G. Bott, S. J. Lippard, Organometallics 1993, 12, 592;
- 11dR. N. Vrtis, S. G. Bott, S. J. Lippard, Organometallics 1992, 11, 270–277;
- 11eR. N. Vrtis, S. G. Bott, R. L. Rardin, S. J. Lippard, Organometallics 1991, 10, 1364–1373;
- 11fP. A. Bianconi, S. J. Lippard, C. P. Rao, R. N. Vrtis (Massachusetts Institute of Technology, USA). Application: US, 1991, pp. 17;
- 11gR. N. Vrtis, S. J. Lippard, Isr. J. Chem. 1990, 30, 331–341;
- 11hR. N. Vrtis, S. Liu, C. P. Rao, S. G. Bott, S. J. Lippard, Organometallics 1991, 10, 275–285;
- 11iR. N. Vrtis, C. P. Rao, S. G. Bott, S. J. Lippard, J. Am. Chem. Soc. 1988, 110, 7564–7566;
- 11jR. N. Vrtis, C. P. Rao, S. Warner, S. J. Lippard, J. Am. Chem. Soc. 1988, 110, 2669–2670;
- 11kP. A. Bianconi, R. N. Vrtis, C. P. Rao, I. D. Williams, M. P. Engeler, S. J. Lippard, Organometallics 1987, 6, 1968–1977.
- 12H. Braunschweig, Q. Ye, A. Vargas, R. D. Dewhurst, K. Radacki, A. Damme, Nat. Chem. 2012, 4, 563–567.
- 13N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457–2483.
- 14G. Schmid, W. Meyer-Zaika, R. Böse, N. Augart, Angew. Chem. 1988, 100, 956–957; Angew. Chem. Int. Ed. Engl. 1988, 27, 952–953.
- 15I. R. Crossley, A. F. Hill, A. C. Willis, Organometallics 2007, 26, 3891–3895.
- 16CCDC 898073, 898074, and 898075 contain the supplementary crystallographic data for Compound 2. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
- 17Geometry optimization and spectroscopic data were calculated for complex 2. Calculations on orbital analyses and mechanistic studies were carried out using smaller model compounds. See the Supporting information for details on computations.
- 18
- 18aH. Braunschweig, M. Burzler, R. D. Dewhurst, K. Radacki, F. Seeler, Z. Anorg. Allg. Chem. 2008, 634, 1875–1879;
- 18bH. Braunschweig, M. Burzler, T. Kupfer, K. Radacki, F. Seeler, Angew. Chem. 2007, 119, 7932–7934; Angew. Chem. Int. Ed. 2007, 46, 7785–7787.
- 19Searches were conducted on The Cambridge Structural Database (CSD).
- 20
- 20aC. Klöfkorn, M. Schmidt, T. Spaniol, T. Wagner, O. Costisor, P. Paetzold, Chem. Ber. 1995, 128, 1037–1043;
- 20bH. Jacobsen, H. Berke, S. Döring, G. Kehr, G. Erker, R. Fröhlich, O. Meyer, Organometallics 1999, 18, 1724–1735;
- 20cC. M. Mömming, G. Kehr, B. Wibbeling, R. Fröhlich, G. Erker, Dalton Trans. 2010, 39, 7556–7564;
- 20dM. Tamm, T. Lügger, F. E. Hahn, Organometallics 1996, 15, 1251–1256.
- 21
- 21aS. Hermanek, Chem. Rev. 1992, 92, 325–362;
- 21bH. Nöth, NMR, 14: Nuclear Magnetic Resonance Spectroscopy of Boron Compounds, Springer-Verlag, Berlin, Heidelberg, New York, 1978.
10.1007/978-3-642-66757-2 Google Scholar
- 22
- 22aJ. A. Bohmann, F. Weinhold, T. C. Farrar, J. Chem. Phys. 1997, 107, 1173–1184;
- 22bU. Fleischer, Deuterium and Shift Calculation, Springer, Berlin, 1991.
10.1007/978-3-642-75932-1 Google Scholar
- 23F. A. Cotton, Prog. Inorg. Chem. 1976, 21, 1–28.
- 24
- 24aE. O. Fischer, W. Schambeck, F. R. Kreissl, J. Organomet. Chem. 1979, 169, C 27–C30;
- 24bE. O. Fischer, W. Schambeck, J. Organomet. Chem. 1980, 201, 311–318.
