Materials
| Name | Company | Catalog Number | Comments |
| Materials | |||
| Lithium wire (in mineral oil) | Aldrich | 278327-100G | >98% |
| 2-bromo-2-butene (mixture of cis/trans isomers) | Acros | 200016-364 | 98%, dried over molecular sieves from an oven overnight before use |
| Hexanes | Millipore | HX0299-3 | GR ACS, used as received |
| Ethyl actetate | Millipore | EX0240-3 | GR ACS, dried over molecular sieves from an oven overnight before use |
| Ammonium chloride | Aldrich | 213330-2.5kg | ACS Reagent |
| Diethyl ether | Millipore | EX0190-5 | GR ACS, collected from a solvent purification system before use |
| Magnesium sulfate | Aldrich | 793612-500g | Anhydrous, reagent grade |
| p-toluene sulfonic acid monohydrate | Fisher | A320-500 | ACS Certified |
| Sodium bicarbonate | Fisher | 5233-500 | ACS Certified |
| Sodium carbonate | Amresco | 0585-500g | |
| Ruthenium(III) chloride trihydrate | Pressure Chemical | 4750 | 40% Metal |
| Iridium(III) chloride hydrate | Pressure Chemical | 5730 | 53% Metal |
| Methanol | Avantor | 3016-22 | AR ACS, distilled from Mg before use |
| Pentane | J. T. Baker | T007-09 | >98%, dried with a solvent purification system before use |
| Chloroform-d | Aldrich | 151823-150G | 99.8 atom % D |
| Molecular sieves 4 Å | Aldrich | 208590-1KG | dried in an oven at 140 °C before use |
| Celite 545 | Acros | AC34967-0025 | dried in an oven at 140 °C before use |
| Name | Company | Catalog Number | Comments |
| Equipment | |||
| Schlenk line, with vacuum and inert gas manifolds | Custom | NA | Used in Preps 1-4 |
| Solvent transfer manifold | Chemglass | AF-0558-01 | Used in 2.2 |
| Airfree filter funnel | Chemglass | AF-0542-22 | Used in 3.1.3 |
| Glovebox | Vacuum Atmospheres | OMNI | Used in 3.2.2 |
References
- Kealy, T. J., Pauson, P. L. A new type of organo-iron compound. Nature. 168, 1039-1040 (1951).
- Wilkinson, G., Rosenblum, M., Whiting, M. C., Woodward, R. B. The structure of iron bis-cyclopentadienyl. J. Am. Chem. Soc. 74, 2125-2126 (1952).
- Fischer, E. O., Pfab, W. Z. Cyclopentadien-Metallkomplexe, ein neuer Typ metallorganischer Verbindungen. Z. Naturforsch. 76, 377-379 (1952).
- Pauson, P. L. Ferrocene-how it all began. J. Organomet. Chem. 637-639, 3-6 (2001).
- Lauher, J. W., Hoffmann, R. Structure and chemistry of bis(cyclopentadienyl)-MLn complexes. J. Am. Chem. Soc. 98, 1729-1742 (1976).
- Resa, I., Carmona, E., Gutierrez-Puebla, E., Monge, A. Decamethyldizincocene, a stable compound of Zn(I) with a Zn-Zn bond. Science. 305, 1136-1138 (2004).
- Brintzinger, H., Bercaw, J. E. Nature of so-called titanocene, (C10H10Ti)2. J. Am. Chem. Soc. 92, 6182-6185 (1970).
- King, R. B. Some applications of metal carbonyl anions in the synthesis of unusual organometallic compounds. Acc. Chem. Res. 3, 417-427 (1970).
- Chirik, P. J. Group 4 transition metal sandwich complexes: still fresh after almost 60 years. Organometallics. 29, 1500-1517 (2010).
- Bengali, A. A., Schultz, R. H., Moore, C. B., Bergman, R. G. Activation of the C-H bonds in neopentane and neopentane-d12 by (η5-C5(CH3)5)Rh(CO)2: Spectroscopic and temporal resolution of rhodium-krypton and rhodium-alkane complex intermediates. J. Am. Chem. Soc. 116, 9585-9589 (1994).
- Shima, T., Hu, S., Luo, G., Kang, X., Luo, Y., Hou, Z. Dinitrogen cleavage and hydrogenation by a trinuclear titanium polyhydride complex. Science. 340, 1549-1552 (2013).
- Negishi, E. -I., Takahashi, T. Alkene and alkyne complexes of zirconocene. Their preparation, structure, and novel transformations. Bull. Chem. Soc. Jpn. 71, 755-769 (1998).
- Rosenthal, U., Burlakov, V. V., Arndt, P., Baumann, W., Spannenberg, A. The titancocene complex of bis(trimethylsilyl)acetylene: Synthesis, structure, and chemistry. Organometallics. 22, 884-900 (2003).
- Jordan, R. F., Bradley, P. K., LaPointe, R. E., Taylor, D. F. Cationic zirconium catalysts for carbon-carbon bond forming chemistry. New J. Chem. 14, 505-511 (1990).
- Ewen, J. A. Symmetry rules and reaction mechanisms of Ziegler-Natta catalysts. J. Mol. Catal. 128, 103-109 (1998).
- Manriquez, J. M., Bercaw, J. E. Preparation of a dinitrogen complex of bis(pentamethylcyclopentadienyl)zirconium(II). Isolation and protonation leading to the stoichiometric reduction of dinitrogen to hydrazine. J. Am. Chem. Soc. 96, 6229-6230 (1974).
- Brintzinger, H. H., Bercaw, J. E. Bis(pentamethylcyclopentadienyl)titanium(II). Isolation and reactions with hydrogen, nitrogen, and carbon monoxide. J. Am. Chem. Soc. 93, 2045-2046 (1971).
- Lehman, M. C., Gary, J. B., Boyle, P. D., Sanford, M. S., Ison, E. A. Effect of solvent and ancillary ligands on the catalytic H/D exchange reactivity of Cp*IrIII(L) complexes. ACS Catal. 3, 2304-2310 (2013).
- Pitman, C. L., Finster, O. N. L., Miller, A. J. M. Cyclopentadiene-mediated hydride transfer from rhodium complexes. Chem. Commun. 52, 9105-9108 (2016).
- Tarantino, K. T., Miller, D. C., Callon, T. A., Knowles, R. R. Bond-weakening catalysis: Conjugate aminations enabled by the soft homolysis of strong N-H bonds. J. Am. Chem. Soc. 137, 6440-6443 (2015).
- Bolig, A. D., Brookhart, M. Activation of sp3 C-H bonds with cobalt(I): Catalytic synthesis of enamines. J. Am. Chem. Soc. 129, 14544-14545 (2007).
- Hung-Low, F., Tye, J. W., Cheng, S., Bradley, C. A. sp2 C-H activation of dimethyl fumarate by a [(Cp*Co)2-µ-(η4:η4-toluene)] complex. Dalton Trans. 41 (26), 8190-8197 (2012).
- Hung-Low, F., Krogman, J. P., Tye, J. W., Bradley, C. A. Development of more labile low electron count Co(I) sources: mild, catalytic functionalization of activated alkanes using a [(Cp*Co)2-µ-(η4:η4-arene)] complex. Chem. Commun. 48 (3), 368-370 (2012).
- Andjaba, J. M., Tye, J. W., Yu, P., Pappas, I., Bradley, C. A. Cp*Co(IPr): synthesis and reactivity of an unsaturated Co(I) complex. Chem. Commun. 52, 2469-2472 (2016).
- Fendrick, C. M., Schertz, L. D., Mintz, E. A., Marks, T. J. Large-scale synthesis of 1,2,3,4,5-pentamethylcyclpentadiene. Inorg. Synth. 29, 193-198 (1992).
- Threlkel, R. S., Bercaw, J. E. A Convenient synthesis of alkyltetramethylcyclopentadienes and phenyltetramethylcyclopentadiene. J. Organomet. Chem. 136, 1-5 (1977).
- Manriquez, J. M., Fagan, P. J., Schertz, L. D., Marks, T. J. 1,2,3,4,5-pentamethylcyclopentadiene. Inorg Synth. 28, 317-320 (1990).
- Threlkel, R. S., Bercaw, J. E., Seidler, P. F., Stryker, J. M., Bergman, R. G. 1,2,3,4,5-pentamethylcyclopentadiene. Org. Synth. 65, (1987).
- Koelle, U., Kossakowski, J. Di-µ-chloro-bis[(η5-pentachlororuthenium(III)], [Cp*RuCl2]2 and Di-µ-methoxo-bis(η5-pentamethylcyclomethylcyclopentadienyl) diruthenium(II), [Cp*RuOMe]2. Inorg. Synth. 29, 225-228 (1992).
- White, C., Yates, A., Maitlis, P. M. η5-pentamethylcyclopentadienyl)rhodium and -iridium compounds. Inorg. Synth. 29, 228-234 (1992).
- Andersen, R. A., Blom, R., Boncella, J. M., Burns, C. J., Volden, H. V. The thermal average molecular structures of bis(pentamethylcyclopentadienyl)magnesium(II), -calcium(II), and -ytterbium(II) in the gas phase. Acta Chem. Scand. 41A, 24-35 (1987).
- Gross, J. H., et al. Liquid injection field desorption/ionization of reactive transition metal complexes. Anal. Bioanal. Chem. 386 (1), 52-58 (2006).
