Ing and would be the HOMO (z-axis along the Mo-oxo bond, and x-axis bisects the dithiolene ligands). There is a big HOMO/LUMO gap of 4.1 eV. The LUMO is close to the practically degenerate Mo dxz/yz set, which can be strongly -antibonding to both the oxo atom and dithiolene ligands (i.e., includes considerable S p character), therefore the low power peak at 2472.5 eV in Figure 2A is assigned as the S 1s Mo dxz/yz transitions. The calculated total S 3p character in these two MOs is 31 , even though experimentally, the S pre-edge intensity gives 38 . The Mo dz2 and Mo dxy orbitals are antibonding to the ligands and therefore at higher energies. On the basis of your calculation shown inFigure 3A, the 2473.three eV peak is assigned because the S 1s Mo dxy/dz2 transitions. The total S 3p covalency is 59 each experimentally and computationally. Inside the [MoIV(OSi)(bdt)2]- reference complex, dz2 and dxy are well separated in power together with the dxy at higher power by 1 eV (see figure S2). Inside the [MoIVO(bdt)2]2- complicated, the dz2 is shifted to larger power, close to dxy resulting from the strong axial Mo-oxo bond. From our previous studies on the Ni and Mo bis-dithiolene complexes, the 2473.7 eV peak in Figure 2A is assigned as the S 1s C-S */* intradithiolene ligand transitions.40,41 As shown in Figure four, for the six-coordinate [MoVIO2(bdt)2]2- complicated, the z-axis is defined as bisecting the O-Mo-O angle, the x-axis is perpendicular to z and within the O-Mo-O plane, as well as the y-axis is perpendicular to this plane. For this cis bisoxo Mo complex, the energies of the Mo dorbitals are dominated by their / bonding interactions together with the two strong oxo donor ligands. The six 2p-orbitals around the 2 oxo atoms type six combinations: the out of plane + and -, in-plane + and -, and +, -; indicates perpendicular for the O-Mo-O plane even though indicates along the bond, and the +/- subscripts indicate the symmetric and antisymmetric combinations of your specific O 2p-orbitals. The in-plane – is nonbonding. The out-of-plane + and -, and in-plane + interact together with the d orbitals on Mo, with all the in-plane + interaction being the strongest because of its increased overlap with all the Mo (dx2-z2) (see Figure 3).(2-Fluoro-6-methylphenyl)boronic acid site Thus, the low energy peak at 2471.two eV in Figure 2C is assigned as the combined set of transitions in the S 1s Mo dyz (that interacts using the outof-plane oxo +) plus the S 1s Mo(dy2) (that interacts with all the out-of-plane oxo -).Price of 1234616-13-7 Experiment gives 33 S p character, even though the DFT calculation includes a total of 31 S 3p character in these two transitions.PMID:22664133 The peak at 2472.2 eV, which can be 1 eV to higher energy, is assigned as S 1s Mo(dx2-z2) (that interacts with in-plane oxo +) transition. Experimentally, this transition has 15 S 3p character, although the calculation gives 10 . The MOs with oxo character are strongly antibonding and thus at larger energy. The 2473.0 eV peak is assigned because the S 1s Mo(dx2-dy2) (antibonding with oxo atoms +). The S covalency is 53 from calculation vs 38 from experiment. The S 1s Mo(dxz) (antibonding with oxo atoms -) transition is calculated to be 3.8 eV above the LUMO,dx.doi.org/10.1021/ja503316p | J. Am. Chem. Soc. 2014, 136, 9094-Journal on the American Chemical Society overlapping the rising edge and thus couldn’t be experimentally resolved. Computationally, this transition has 23 S p character. Finally, around the basis of our previous studies5, the 2473.six eV peak is assigned as S 1s C-S */* intradithiolene ligand transitions. Comparisons on the DFT calculations with S K-edge XAS experi.
