SYNTHESIS AND REACTIVITY OF FUNCTIONALIZED RHENIUM SILYL COMPLEXES (ETA-5-C5H5)RE(NO)(PPH3)(SIR2X) - ANIONIC REARRANGEMENTS LEADING TO THE DISILAMETALLACYCLE (ETA-5-C5H4SI(CH3)2)RE(NO)(PPH3)(SI(CH3)2)
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Reaction of Li+[(5-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 (5-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 (5-C5H4Si(CH3)3) (8), which rapidly rearranges at -78 C to silylcyclopentadienyl complex Li+[(5-C5H4Si(CH3)3)Re(NO)(PPh3)]- (9). Addition of CH3OTf gives methyl complex (5-C5H4Si(CH3)3)Re(NO)(PPh3)(CH3) (10, 72%). Similar reaction of 7 and n-BuLi/TMEDA gives (5-C5H4Li)Re(NO)(PPh3)(Si(CH3)2Si(CH3)2Cl) (13), which rearranges at -24 C to Li+[(5-C5H4Si(CH3)2Si(CH3)2Cl)Re(NO)(PPh3)]- (14). Upon warming, 14 cyclizes to disilametallacycle (5-C5H4Si(CH3)2)Re(NO)(PPh3)(Si(CH3)2) (15, 53%). 1988, American Chemical Society. All rights reserved.