Synthesis of the cobalt-alkyne complex (η5-C5H5)(PPh3)Co{η2-(Me3Si)CC(CO2Et)} and structural characterization of trimethylsilyl substituted cobaltacyclopentadiene complexes derived therefrom

Autor: Bunker, KD, Rheingold, AL, Moore, CE, Aubrey, M, O'Connor, JM
Jazyk: angličtina
Rok vydání: 2014
Zdroj: Bunker, KD; Rheingold, AL; Moore, CE; Aubrey, M; & O'Connor, JM. (2014). Synthesis of the cobalt-alkyne complex (η5-C5H5)(PPh3)Co{η2-(Me3Si)CC(CO2Et)} and structural characterization of trimethylsilyl substituted cobaltacyclopentadiene complexes derived therefrom. Journal of Organometallic Chemistry, 749, 100-105. doi: 10.1016/j.jorganchem.2013.09.002. UC San Diego: Retrieved from: http://www.escholarship.org/uc/item/1p6184kv
DOI: 10.1016/j.jorganchem.2013.09.002.
Popis: The reaction of (η5-C5H5)Co(PPh3)2with TMSCC(CO2Et) leads to the formation of the cobalt-alkyne complex (η5-C5H5) (PPh3)Co{η2-(Me3Si)CC(CO2Et)} (6). In benzene-d6solution containing PPh3, 6 undergoes slow conversion to the cobaltacyclopentadiene complex (η5-C5H5)(PPh3)Co{κ2-(TMS) CC(CO2Et)C(TMS)C(CO2Et)} (7, TMS = SiMe3). Alternatively, reaction of 6 and PhCCPh forms the metallacyclopentadiene regioisomers (η5-C5H5)(PPh3)Co{κ2-(R1)CC(R2)C(Ph)=C(Ph)} [9-major, R1= SiMe3, R2= CO2Et; 9-minor, R1= CO2Et, R2= SiMe3). The metallacycle substitution pattern in 9-major and 9-minor is readily deduced from the1H NMR spectral resonances of the diastereotopic ethoxycarbonyl hydrogens. When the diastereotopic hydrogens of the ethoxycarbonyl have similar chemical shifts the ester is situated on the β-carbon of the metallacycle. When the methylene hydrogens give rise to well-separated resonances the ethoxycarbonyl is situated on the α-carbon of the metallacycle. The solid state structures of 7 and 9-major were determined by X-ray crystallography. © 2013 Elsevier B.V. All rights reserved.
Databáze: OpenAIRE