Divergent kinetic and thermodynamic acidity in organotransition-metal hydride complexes: synthesis, structure, and reactivity of the rhenium anion of Li+ [(.eta.-C5H5)Re(NO)(PPh3)]-. Academic Article uri icon

abstract

  • Reaction of hydride complex (η5-C5H5)Re(NO)(PPh3)(H) (1) and n-BuLi/TMEDA (THF, -78 °C) gives (η5-C5H4Li)Re(NO)(PPh3)(H) (Li+ -8), as shown by 31P NMR monitoring, deuterium labeling, and methylation (CH3OSO2CF3, -78 °C) to (η5-C5H4CH3)Re(NO)(PPh3)(H) (9, 52%). Complex Li+-8 rearranges to the rhenium anion of Li+[(η5-C5H5)-Re(NO)(PPh3)]−(Li+-3; -32 °C, 0.5 h) with ΔH‡ = 11.3 ±0.5 kcal/mol, ΔS‡ = -26.2 ± 1.4 eu, and kH/kD(-22.4 °C) = 1.16 ± 0.08. Crossover experiments show hydrogen migration to be intramolecular, and K+-8 rearranges ca. 104 faster than Li+-8 at -91.6 °C. Equilibration experiments show the η5-C5H5 and ReH proton pKa's (THF) in 1 to be ca. 36 and 26–30, respectively. Thus, the less acidic proton is abstracted kinetically, and a rationale is proposed. Reactions of Li+-3 with alkylating agents (CH3I, n-C4H9I, ClCH2CH=CH2, ClCH2COPh), benzoic anhydride, and D2O give the corresponding alkyl, acyl, and deuteride complexes (56-90%). IR data show Li+-3 to be a mixture of three ion pairs in THF. Pentamethyl analogue (η5-C5Me5)Re(NO)(PPh3)(H) (13) is prepared from methyl complex (η5-C5Me5)Re(NO)(PPh3)(CH3) (11; HCOOH, then 110 °C; 43%). Reaction of 13 and n-BuLi/K+-t-BuO− gives principally K+[(η5-C5Me5)Re(NO)(PPh3)]−, as assayed by 31P NMR and methylation (CH3I) to 11. © 1988, American Chemical Society. All rights reserved.

author list (cited authors)

  • Crocco, G. L., & Gladysz, J. A.

citation count

  • 28

publication date

  • August 1988