A kinetic investigation of carbon dioxide insertion processes involving anionic tungsten-alkyl and -aryl derivatives: effects of carbon dioxide pressure, counterions, and ancillary ligands. Comparisons with migratory carbon monoxide insertion processes Academic Article uri icon

abstract

  • A mechanistic investigation of the 1, 2-addition of carbon dioxide to tunesten-alkvl and -arvl derivatives. namely cis-RW(CO)4L-(R = Me, Et, and Ph; L = CO, PMe3, and P(OMe)3), to provide metallocarboxylates is reported. The reaction is shown to obey second-order kinetics, first order in anionic metal substate and first order in carbon dioxide. A concerted reaction pathway involving an attack of the nucleophilic RW(CO)5-ion at the electrophilic carbon or carbon oxygen center of CO2is proposed. This proposal is supported by the dependence of the rate of these reactions on carbon monoxide and the nature of the metal center, the activation parameters, and the observed retention of configuration at the a-carbon atom. Replacement of carbon monoxide in the metal's coordination sphere by more electron-donating phosphite or phosphine ligands results in a significant enhancement of the rate of CO2insertion into the tungsten-carbon bond. For example, the rate of CO2insertion into cis-CH3W(CO)4PMe3-is 243 times greater than that in CH3W(CO)5-The molecular structure of [PPN] [cis-CH3W(CO)4PMe3] was determined at -99 °C and W-CH3bond distance of 2.18 (3) Å was found to be somewhat shorter than that seen in the isoelectronic neutral Re-CH3analogue (2.308 (17) Å). The compound crystallizes in the monoclinic space group Cc with a = 16.538 (8) Å, b = 17.102 (9) Å, c = 16.106 (7) Å, β = 115.26 (3)°, and V- 4119.7 Å3. Unlike the carbon dioxide insertion reactions which did not exhibit a large rate dependence on the nature of the R group, migratory carbon monoxide insertion reactions involving these anionic RW(CO)5-derivatives display significant retardation with decreasing electron-donating ability of the R substituent. Further mechanistic comparisons of carboxylation and carbonylation processes are provided. © 1985, American Chemical Society. All rights reserved.

author list (cited authors)

  • Darensbourg, D. J., Hanckel, R. K., Bauch, C. G., Pala, M., Simmons, D., & White, J. N

complete list of authors

  • Darensbourg, Donald J||Hanckel, Rebecca Kudaroski||Bauch, Christopher G||Pala, Magdalena||Simmons, Debra||White, J Nicole

publication date

  • January 1, 1985 11:11 AM