Bicymantrenyl chemistry: 5. * Substitution reactions in Cp rings of (CO)3MnC5H4C5H 4Mn(CO)2PPh3 complex

Article abstract of DOI:10.1007/BF02495366

The complex (CO)₃MnC₅H₄C₅H ₄Mn(CO)₂PPh₃ (2) can be involved in electrophilic reactions such as hydrogen-deuterium exchange with CF₃COOD in CH₂Cl₂ and acetylation with a MeCOCl-AlCl₃ mixture. In both cases, the substituent (D or MeCO) only enters the C₅H₄Mn(CO)₂PPh₃ ring. Metallation of 2 with BuLi (THF, -60°C) occurs exclusively in the C₅H₄Mn(CO)₃ ring. Quenching of Li-containing derivatives with DMF results in a mixture of two isomeric aldehydes with the substituent in position 2 or 3. Reduction of 3-aldehyde with NaBH₄ gives the corresponding carbinol (6b). Metallation of the latter followed by quenching with DMF gives hydroxyaldehyde (CO)₂PPh₃MnC₅H₄C₅H ₂(CH₂OH)(CHO)Mn(CO)₃.