Synthesis and reactivity of functionalized rhenium silyl complexes (.eta.5-C5H5)Re(NO)(PPh3)(SiR2X). Anionic rearrangements leading to the disilametallacycle [cyclic] [.eta.5-C5H4Si(CH3)2]Re(NO)(PPh3)[Si(CH3)2] Academic Article uri icon


  • Reaction of Li+[(η5-C5H5)Re(NO)(PPh3)]-(3) with silicon electrophiles (CH3)3SiOTf, (CH3)2SiHCl, (CH3)2Si(CH=CH2)OTf, and Cl(CH3)2SiSi(CH3)2Cl gives functionalized silyl complexes (η5-C6H6)Re-(NO)(PPh3)(Si(CH3)2X) (X = CH3 (4), H (5), CH=CH2 (6), and Si(CH3)2Cl (7)) in 83-21% yields after workup. Reaction of 4 and n-BuLi/TMEDA gives, as assayed by 31P NMR, lithiocyclopentadienyl complex (η5-C5H4Si(CH3)3) (8), which rapidly rearranges at -78 °C to silylcyclopentadienyl complex Li+[(η5-C5H4Si(CH3)3)Re(NO)(PPh3)]- (9). Addition of CH3OTf gives methyl complex (η5-C5H4Si(CH3)3)Re(NO)(PPh3)(CH3) (10, 72%). Similar reaction of 7 and n-BuLi/TMEDA gives (η5-C5H4Li)Re(NO)(PPh3)(Si(CH3)2Si(CH3)2Cl) (13), which rearranges at -24 °C to Li+[(η5-C5H4Si(CH3)2Si(CH3)2Cl)Re(NO)(PPh3)]- (14). Upon warming, 14 cyclizes to disilametallacycle (η5-C5H4Si(CH3)2)Re(NO)(PPh3)(Si(CH3)2) (15, 53%). © 1988, American Chemical Society. All rights reserved.

author list (cited authors)

  • Crocco, G. L., Young, C. S., Lee, K. E., & Gladysz, J. A.

citation count

  • 31

publication date

  • October 1988