97689-39-9Relevant articles and documents
Methylidyne-alkyne coupling on triruthenium clusters and hydrogenation of cluster-bound 1,3-dimetalloallyl units. A new model for Fischer-Tropsch chain growth
Beanan, Lawrence R.,Keister, Jerome B.
, p. 1713 - 1721 (2008/10/08)
Alkylidyne-alkyne coupling occurs upon reaction of H3Ru3(μ3-CX)(CO)9 (X = OMe, Me, Ph, or CH2CH2CMe3) at 25 °C or HRu3(μ-CX)(CO)10 (X = OMe) at 60 °C with alkynes R1C2R2, forming 1,3-dimetalloallyl clusters HRu3(μ3-η3-XCCRCR)(CO)9 (X = OMe, (R1, R2) = (H, H), (Me, Me), (Ph, Ph), (H, Ph), (H, CMe3), (H, n-Bu), (H, CO2Me), (Ph, CO2Me), (H, OEt); X = Ph, (R1, R2) = (Ph, Ph); X = Me, (R1, R2) = (Me, Me); X = CH2CH2CMe3, (R1, R2) = (Ph, Ph)) in yields of 15-90%. In an analogous fashion, HOs3(μ-COMe)(CO)10 and PhC2Ph yield HOs3(μ3-η3-MeOCCPhCPh)(CO)9. One equivalent of the appropriate cis-alkene is formed from reduction of alkyne by H3Ru3(μ3-CX)(CO)9. With unsymmetrical alkynes the relative amounts of the two possible regioisomers depend upon the alkyne substituents. Coupling from either H3R3(μ3-COMe)(CO)9 or HRu3(μ-COMe)(CO)10 forms HRu3(μ3-η3-MeOCCR1CR 2)(CO)9 in the relative amounts (R1, R2) = (H, Ph)/(Ph, H), 3:1, (H, n-Bu)/(n-Bu, H), 2:1, (H, CMe3,)/(CMe3, H), 20:1, (H, CO2Me)/(CO2Me, H), 2:1, (H, OEt)/(OEt, H), 1:0, (Me, C7-H15, Me), 3:1, and (CO2Me, Ph)/(Ph, CO2Me), 2:1. Hydrogenation (90 °C, 1-4 atm) of HRu3(μ3-η3MeOCCR1CR 2)(CO)9 ((R1, R2) = (H, H), (H, CMe3), (Me, Me), (Ph, Ph), (H, OEt), (H, Ph), (H, n-Bu), (n-Bu, H), (H, CO2Me)) produces in each case the corresponding H3Ru3(μ3CCHR1CH2R 2)(CO)9 in yields of 6-43%; also formed are substantial quantities of H4Ru4(CO)12. Hydrogenation of DRu3(μ3-η3-MeOCCHCCMe 3)(CO)9 produces exclusively H3Ru3(μ3-CCH2CHDCMe 3)(CO)9. This alkylidyne-alkyne coupling and subsequent hydrogenation to form an alkylidyne of longer carbon chain length suggests a mechanism to account for 2-methylated hydrocarbon products in the Fischer-Tropsch reaction.
