摘要:
The complex (CO)(3)MnC5H4C5H4Mn(CO)(2)PPh3 (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)(2)PPh3 ring. Metallation of 2 with BuLi (THF, -60 degrees 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)(2)PPh3MnC5H4C5H2(CH2OH)(CHO)Mn(CO)(3).