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Calculations were carried out with the Gaussian03 series of programs using the B3LYP functional. The basis set for Rh and P atoms was LANL2DZ, which in the case of P was supplemented by a d shell. For the atoms O and N directly attached to rhodium and the ester group of the carbene we used the 6-31G(d) basis set; for the rest of the atoms the 6-31G basis set was used. See the Supporting Information for further details.
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Calculations were carried out with the Gaussian03 series of programs using the B3LYP functional. The basis set for Rh and P atoms was LANL2DZ, which in the case of P was supplemented by a d shell. For the atoms O and N directly attached to rhodium and the ester group of the carbene we used the 6-31G(d) basis set; for the rest of the atoms the 6-31G basis set was used. See the Supporting Information for further details.
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17
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47249091746
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3 ligands axially bound to 1a-c show the same ordering of frontier molecular orbitals and an analogous correlation between the HOMO energies and the oxidation potentials (see Table S5 and Figure S2 in the Supporting Information).
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3 ligands axially bound to 1a-c show the same ordering of frontier molecular orbitals and an analogous correlation between the HOMO energies and the oxidation potentials (see Table S5 and Figure S2 in the Supporting Information).
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Glendening, E. D, Reed, A. E, Carpenter, J. E, Weinhold, F. Gaussian03 Program; Gaussian, Inc, Wallingford, CT, 2004; NBO, version 3.1
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22
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The rotational barriers are expected to be very low because there are two filled Rh 4dxz and 4dxy orbitals available for back-donation to the carbene vacant 2p orbital.17 Thus, for the sake of simplicity, we base our discussion only on the lowest energy minimum for each ligand
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17 Thus, for the sake of simplicity, we base our discussion only on the lowest energy minimum for each ligand.
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