Simple Organometallic Alcohols: Synthesis of (C5H4OH)Mn(CO)3 (Hydroxycymantrene) and (C5H4OH)W(CO)3CH3

The reaction of tert-butyldimethylsilyl triflate with cyclopent-2-enone and 3,4-dimethylcyclopentenone, respectively, gives siloxycyclopentadienes in yields >90%, whose deprotonation and reaction with BrMn(CO) 3 (py) 2 or W(CO) 3 (CH 3 CN) 3 /MeI generates (CpOSi t BuMe 2 )Mn(CO) 3 and (CpOSi t BuMe 2 )W(CO) 3 Me. Cleavage of the organometallic silyl ether with NBu 4 F results in the formation of the previously unknown alcohols (C 5 H 4 OH)Mn(CO) 3 and (C 5 H 4 OH)W(CO) 3 Me in 80−90% yield, from which the corresponding ethers can be synthesized.