In the free energy profile calculation of Pd-catalysis, I included the role role of copper(II) acetate as a monomer, such that the relevant heterodimetallic TS (Pd-Cu complex) is a neutral spin doublet, however, the ground state (g.s.) of copper(II) acetate, using dimeric species, is a neutral spin triplet. If I use half of the g.s. energy of copper(II) acetate dimer in the free energy calculations, is it valid, since the spins will be different? Should I have used the monomeric doublet copper(II) acetate in the energy calculations? One example I found is that the authors used the dimeric Cu(II) species in both the TS and as the starting material, thus circumventing the dilemma: Article Cooperative Reductive Elimination: The Missing Piece in the ...
my system, however, is too big for me to include another Cu(OAc)2 monomer and I cannot see any relevant metal-metal or metal-ligand interactions if I do.
Any suggestions or directions to relevant papers are most appreciated!
Hi Uttam,
thanks for your reply. There are other species that I looked at for the system, including a Pd-Ag heterometallic TS, we want to put them all on the same profile for comparison, so the common SM is 1/2 *[Pd(OAc)2]3, while Ag and Cu additives are then involved. Following your suggestion we would still need to be able to compare the energy of the Pd-Cu heterometallic reactant to the other species in our system.
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