DEPROTONATION OF RHENIUM TERMINAL ACETYLIDE COMPLEXES OF THE FORMULA (ETA-5-C5R5)RE(NO)(PPH3)(CCH) - GENERATION AND REACTIVITY OF RHENIUM LITHIUM C2 COMPLEXES
Academic Article
Overview
Identity
Additional Document Info
Other
View All
Overview
abstract
Reactions of methyl complexes (5-C5R4R)Re(NO)(PPh3)(CH3) (R/R H/H, H/CH3, CH3/CH3) with HBF4OEt2, chlorobenzene, and RCCH (R H, CH3) give terminal alkyne complexes [(5-C5R4R)-Re(NO)(PPh3)(RCCH)]+BF4 (7287%). When R CH3, equilibria with methylvinylidene complexes [(5-C5R4R)Re(NO)(PPh3)(CCHCH3)]+BF4 can be effected at 9065 C (7599% conversion). Treatment of the alkyne or vinylidene complexes with t-BuOK+ gives acetylide complexes (5-C5R4R)-Re(NO)(PPh3)(CCR) (R/R/R: 1, H/H/H; 3, H/H/CH3; 11, H/CH3/H; 12, H/CH3/CH3; 2, CH3/CH3/H; 17, CH3/CH3/CH3; 8194%). Reactions of 1 with 1.0 and 2.0 equiv of n-BuLi give the lithiated complexes (5-C5H5)Re(NO) (PPh3) (CCLi) and (5-C5H4Li)Re(NO) (PPh3) (CCLi), respectively, as assayed by 31P NMR and subsequent conversion with CH3I to 3 and 12. Reaction of 1 with 2.0 equiv of n-BuLi and Ph3SnCl gives the stannylated complex (5-C5H4SnPh3)Re(NO)(PPh3)(CCSnPh3) (49%), which upon silica gel chromatography yields (5-C5H4SnPh3)Re(NO)(PPh3)(CCH). Reaction of 2 with n-BuLi gives (5-C5(CH3)5)Re(NO)(PPh3)(CCLi), as assayed by subsequent reactions with CH3I, D2O, Me3SiCl, and Ph3SnCl to give 17 (95%), 2-d1 (88%; 86-89% labeled), (5-C6(CH3)5Re(NO)(PPh3)(CCSi(CH3)3) (86%), and (5-C5(CH3)5)Re(NO)(PPh3)(CCSnPh3) (45%). 1992, American Chemical Society. All rights reserved.
