Kinetics and mechanism of the formation of the bis(ethylidyne) tricobalt cluster Cp*3 Co33 -CCH3 ) 2 from reaction of acetylene with Cp*3 Co32 -H)33 -H)

Journal Article

The paramagnetic tetrahydride cluster Cp*3Co3(μ2-H)3(μ 3-H) (1) reacts with acetylene to ultimately form the bis(ethylidyne) cluster Cp*3Co3(μ3-CCH3) 2 (2). Two kinetically formed intermediates were isolated from the reaction: the diamagnetic mono(ethylidyne) trihydride cluster Cp*3CO3(μ2-H)3(μ 3-CCH3) (3) and the paramagnetic mono(ethylidyne) monohydride cluster Cp*3Co3(μ3-H)(μ 3-CCH3) (4). Cluster 3 loses H2 at 80 °C [ΔG‡ = 29.5(1) kcal mol-1] to generate 4, and 4 reacts with H2 at 80 °C [ΔG‡ = 23.8(1) kcal mol-1] to regenerate 3. A third intermediate in the reaction of 1 with acetylene, the bridging acetylene dihydride cluster Cp*3CO3(μ-H)2(μ 3-η2-HCCH) (5), was detected by 1H NMR spectroscopy at 23 °C and rearranges to form exclusively cluster 4. Cluster 1 reacts with DC≡CD at 80 °C to form Cp*3CO3(μ2-D)(μ 3-CCH2D) (3-CH2D) as the exclusive diamagnetic product. The formation of 3-CH2D is consistent with the presence of the ethylidene dihydride intermediate Cp*3-Co3(μ2-H)2(μ 2-CDCH2D) (III).

Duke Authors

Cited Authors

  • Casey, CP; Hallenbeck, SL; Widenhoefer, RA

Published Date

  • 1995

Published In

  • Journal of the American Chemical Society

Volume / Issue

  • 117 / 16

Start / End Page

  • 4607 - 4622