Homo- and Hetero-Bimetallic Mu(Eta1-O:Eta1-O') Formate Complexes (M- OCHO-M')+PF6-(M,M'=(Eta5-C5H5)(CO)(NO)Re, (Eta5-C5H5)(CO)3W, and (Eta5-C5H5)(CO) 2Fe): Their Synthesis, Solution Lability, and Reactivity Towards Hydride Donors
Abstract
The rhenium and tungsten (eta 1-O) formates Cp(NO)(CO)Re-OC(O)H and Cp(CO)3W-OC(O)H are available through protonolysis (HBF4-HCO2H) of their methyl complexes. These formates, in turn, afford homobimetallic (ReRe) and (WW) mu(eta1-O,O') formates M-OCHO-M+ upon reacting with requisite organometallic Lewis acid (M-H/Ph3C+). Analogous heterobimetallic mu-formates (FpRe) and (FpW) (Fp=Cp(CO)2Fe) also are prepared using similar reaction chemistry. The (ReRe)mu- formate salt is labile in solution; its dissociative equilibrium can be intercepted with FpOC(O)H to give the mixed (FpRe)mu-formate. Tungsten- containing bimetallic mu-formate salts, in contrast, do not reversibly dissociate in solution. Reactions of hydride donors, including Et3BDLi, with Cp(CO)3W-OCHO-W(CO)3Cp+ give only the W formate and Cp(CO)3W-H(D); no evidence was found for hydride (deuteride) adding to the carboxylate carbon of the formate bridge.
Document Details
- Document Type
- Technical Report
- Publication Date
- Oct 03, 1988
- Accession Number
- ADA203025
Entities
People
- Alan R. Cutler
- Chung C. Tso
Organizations
- Rensselaer Polytechnic Institute