Organometallics p. 1537 - 1542 (1985)
Update date:2022-08-03
Topics:
Bianchini, Claudio
Meli, Andrea
The Ni(0) complex (np3)Ni [np3 = tris(2-(diphenylphosphino)ethyl)amine] reacts with formaldehyde to give the paramagnetic Ni(I) formyl complex (np3)Ni(CHO), which decomposes to the diamagnetic Ni(0) carbonyl (np3)Ni(CO). Formaldehyde reacts with the Co(I) hydride (np3)CoH or with the methyl complex (np3)Co(CH3) to give the hydrido carbonyl compound (np3)Co(CO)H. When the latter reactions are carried out in the presence of NaBPh4, the cationic carbonyl [(np3)Co(CO)]BPh4 is formed. Acetaldehyde and propionaldehyde react with (np3)CoH yielding the corresponding paramagnetic η1-acyl complexes (np3)Co(COCH3) and (np3)Co(COC2H5). The reactivity of the acetyl derivative toward nucleophiles and electrophiles is investigated. Nucleophiles displace the acetyl ligand to give the corresponding complexes (np3)Co(Nu), whereas electrophiles remove the acetyl ligand to give the [(np3)Co]+ moiety. Possible reaction mechanisms are suggested on the basis of chemical and theoretical data.
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Doi:10.1016/S0040-4039(00)61951-2
(1985)Doi:10.1002/(sici)1521-3765(19981102)4:11<2182::aid-chem2182>3.0.co;2-u
(1998)Doi:10.1021/jo00319a002
(1981)Doi:10.1039/j39690000622
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(2021)Doi:10.1021/jo9811569
(1998)