Significance of Carbenoid Character during the Protonation of Four- and Five-Membered Diruthenacycles Formed from the Reaction of Ru2(Me2PCH2PMe2)2(CO)5 with Dimethyl Acetylenedicarboxylate

Kimberly A. Johnson, Michael D. Vashon, Bahram Moasser, Bridget K. Warmka, Wayne L Gladfelter

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

Protonation of the diruthenacyclobutene Ru2(dmpm)2(CO)4[μ-η11-C2(CO2Me)2] (dmpm = bis(dimethylphosphino)methane) resulted in stereoselective formation of the chelated (Z)-alkenyl complex {Ru2(dmpm)2(CO)4[C2(H)(CO2Me)2]}[BF4], as determined by single-crystal X-ray crystallography (P21212 (No. 18) space group, a = 15.61(2) Å, b = 22.67(2) Å, c = 9.34(1) Å, V = 3308(5) Å3, Z = 4). Protonation of the diruthenacyclopentenone Ru2(dmpm)2(CO)4[μ-C(O)C2(CO2Me)2] occurs reversibly at the carbonyl oxygen of the bridging group, giving the corresponding diruthenacyclopentenol. The X-ray crystal structure of the solvated molecule [P21 (No. 4) space group, a = 16.010(7) Å, b = 11.833(6) Å, c = 19.450(8) Å, β = 103.44(3)°, V = 3584(5) Å3, Z = 4) and its unusual blue color suggest a highly delocalized π-system between the two metals. Reaction of the metal hydride [HRu2(dmpm)2-(CO)5][BF4] with dimethyl acetylenedicarboxylate (DMAD) results in formation of a new C-H bond and a σ-bound (E)-alkenyl ligand. This same (E)-alkenyl product can also be formed by addition of CO to and alkene isomerization of the chelated (Z)-alkenyl complex {Ru2(dmpm)2(CO)4[C2(H)(CO2Me)2]}[BF4].

Original languageEnglish (US)
Pages (from-to)461-470
Number of pages10
JournalOrganometallics
Volume14
Issue number1
DOIs
StatePublished - Jan 1995

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