Fischer carbene complexes of cobalt(I) : synthesis and structure
Moeng, Mmushi M.; Malan, Frederick P.; Lotz, Simon; Bezuidenhout, Daniela I. (2021-12-05)
Mmushi M. Moeng, Frederick P. Malan, Simon Lotz, Daniela I. Bezuidenhout, Fischer carbene complexes of cobalt(I): Synthesis and structure, Journal of Molecular Structure, Volume 1252, 2022, 132093, ISSN 0022-2860, https://doi.org/10.1016/j.molstruc.2021.132093
© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/) .
https://creativecommons.org/licenses/by/4.0/
https://urn.fi/URN:NBN:fi-fe202201051214
Tiivistelmä
Abstract
Three different aryl substrates thiophene (ThH), ferrocene (FcH) and p-bromodimethylaniline (p-DMABr) were lithiated and reacted with [Co(CO)₄SnPh₃], according to the Fischer carbene protocol. The products [CoSnPh₃(CO)₃{C(OEt)R}] (R =Th, 1, p-DMA, 2 and R = Fc, 3) were analysed to unravel the role of the aryl carbene substituent in stabilizing intermediates and final products. The ethoxy carbene complexes were aminolysed by in situ generated HNMe₂ to afford [CoSnPh₃(CO)₃{C(NMe₂)R}] (R =Th, 4, p-DMA, 5) and with N,N-dimethylethylenediamine [CoSnPh₃(CO)₃{C(NHCH₂CH₂NMe₂)R}] (R = p-DMA, 6) in high yields. The trigonal Co(CO)₃ in the equatorial plane is very stable and efforts to displace a carbonyl in 6 was unsuccessful, both by heating and irradiation. The role of the aryl carbene substituents in stabilizing the electrophilic carbene carbon was investigated and studied by NMR spectroscopy in solution and single crystal X-ray structure determinations.
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