Synthesis, Structure, and Reactivity of Ruthenium Perfluoropinacolate Complexes#

The chemistry of ruthenium pinacolate complexes has not been well explored. In this work, ruthenium(VI) nitrido perfluoropinacolate (pin F ) complexes have been synthesized and their reactivity has been investigated. Treatment of ( n Bu 4 N)[Ru(N)Cl 4 ] with Na 2 pin F afforded ( n Bu 4 N)[Ru(N)(pin F )Cl 2 ] ( 1 ) that has been used as a starting material for synthesis of Ru(pin F ) complexes. Chloride substitution of 1 with K[N(Ph 2 PQ) 2 ] and Na(L OEt ) (L OEt - = [Co( eta 5 -C 5 H 5 ){P(O)(OEt) 2 } 3 ] - ) afforded [Ru(N)(pin F ){N(Ph 2 PQ) 2 }] ( Q = S ( 2 ), Se ( 3 )) and [(L OEt )Ru(N) (pin F )] ( 4 ), respectively. Nucleophilic attack of 4 with PPh 3 and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (Im Dipp ) gave the Ru(IV) phosphoraneiminate [(L OEt )Ru(NPPh 3 )(pin F )] ( 5 ) and imidazolin-2-iminate [(L OEt )Ru(NIm Dipp )(pin F )] ( 6 ) complexes, respectively. The dichloride analogue of 5 , [(L OEt )Ru(NIm Dipp )Cl 2 ] ( 7 ), has been synthesized and structurally characterized. Oxidation of 7 with NR 3 SbCl 6 ( R = 4-bromophenyl) gave [L OEt RuCl 3 ]SbCl 6 that was co -crystallized with NHIm Dipp . The crystal structures of 1, 2, 4, 5 and 7 have been determined.