Name
Title | ||
|---|---|---|
Mechanisms of norbornadiene dimerization to Binor-S using cationic CoI, RhI, and IrI catalysts |
Abstract | ||
|---|---|---|
We investigated the transition metal-catalyzed reaction mechanisms of NBD dimerization to Binor-S using cationic Co-I, Rh-I, and Ir-I catalysts, using mPW1PW91, mPW1K, and B3LYP density functional methods. Our results indicate that the monomeric metal center has the ability to bind with four double bonds of two NBD molecules with a syn spatial geometry to form a penta-coordinated complex. We designed three possible pathways, but found two of them blocked. The favored pathway involves three steps from the reactant precursor to the product precursor: the first step is the formation of a single bond to connect two NBD units, the second is the alkene insertion leading to the formation of the three-membered ring structure, and the final step is the formation of the final product precursor. Orbital analysis showed metal center dot center dot center dot C-C sigma agostic interaction in the product precursor, which is in agreement with the previous experimental findings. In addition, we found that the solvent and counter-ions had significant effects on the dimerization reactions. (C) 2010 Wiley Periodicals, Inc. J Comput Chem 31: 2248-2257, 2010 |
Year | DOI | Venue |
|---|---|---|
2010 | 10.1002/jcc.21514 | JOURNAL OF COMPUTATIONAL CHEMISTRY |
Keywords | Field | DocType |
bicyclo[2.2.1]hepta-2,5-diene,norbornadiene dimer,dimerization,DFT,Binor-S,solvent effect,counter ion,agostic interaction | Chemistry,Alkene,Norbornadiene,Stereochemistry,Agostic interaction,Cationic polymerization,Double bond,Single bond,Solvent effects,Reaction mechanism | Journal |
Volume | Issue | ISSN |
31 | 12 | 0192-8651 |
Citations | PageRank | References |
0 | 0.34 | 1 |
Authors | ||
5 | ||