Reactivity of formaldehyde and acetaldehyde toward [N(CH2CH2PPh2)3]Ni and [N(CH2CH2PPh2)3]CoH

Article abstract of DOI:10.1021/om00128a009

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.