Synthesis and reactivity of chiral rhenium indenyl complexes of the formula [(.eta.5-C9H7)Re(NO)(PPh3)(X)]n+
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Reaction of (η5-C9H7)Re(CO)3 and NO+BF4- yields [(η6-C9H7)Re(NO)(CO)2]+BF4- (2, 94%), which with PPh3 (C1CH2CH2C1, reflux) gives [(η5-C9H7)Re(NO)(PPh3)(CO)]+BF4- (3, 94%). When 2 is dissolved in acetone, addition products of the formula (η1-C9H7)Re(NO)(CO)2(η1-OC(CH3)2)2 form. Attempted reduction of the CO ligand in 3 yields hydride complexes. However, reaction of 2 and NaBH4 gives (η5-C9H7)Re(NO)(CO)(CH3) (6, 45%), which with PPh3 (C1CH2CH2C1, reflux) yields (η5-C9H7)Re(NO)(PPh3)(CH3) (5, 18%) and (η5-C9H7)Re(NO)-(PPh3)(COCH3) (7, 54%). Reaction of 5 and HBF4·OEt2 in CH2C12 at −80 °C gives the unstable, substitution-labile dichloromethane complex [(η5-C9H7)Re(NO)(PPh3)(ClCH2Cl)]+BF4- (8), which is characterized by NMR. Subsequent addition of acetone or cyclohexanone yields σ-ketone complexes [(η5-C9H7)Re(NO)(PPh3)(η1-0CR2)]+BF4- (82–76%), and addition of CO (250 psi) gives 3 (92%). In another approach to 5 and 8, 3 and NaOCH3 are combined to give (η5-C9H7)Re(NO)(PPh3)(CO2CH3) (11, 92%). Sequential reactions with CH3MgBr and BH3·THF produce 7 (53%) and (η5-C9H7)Re(NO)(PPh3)(CH2CH3) (12, 95%). The latter could not be converted to 8 in high yield. However, reaction of 12 and HI affords (η6-C9H7)Re(NO)(PPh3)(I) (88%), which with CuCH3 gives 5 (62%). © 1993, American Chemical Society. All rights reserved.
author list (cited authors)
Zhou, Y., Dewey, M. A., & Gladysz, J. A.