Igation. TS3 has the lowest energy barrier (12 kcal/mol; TS1 has 21 and TS2 has 20 kcal/mol), which can be extremely equivalent for the H that was measured experimentally (10 kcal/mol).23 You will discover two key points to note about the geometric and electronic structures of those transition states. Initial, TS3 has a P-S interaction involving the phosphorus lone pair donating electron density in to the Mo-based unoccupied d-orbital that may be delocalized onto the oxo and also the S p orbital that is definitely perpendicular for the dithiolene plane (Figure 5B). The P-S distance is three.3 ?plus the P-S MBO is 0.15. This P-S interaction stabilizes the transition state by ten kcal/mol relative to TS1, which has the P lone pair interact only using the oxo p orbital. Second, one of several O(Me)-P-O(Mo) angles in TS3 (and TS1) is practically linear (165?. This was initially noted by Hall and colleagues,18 and attributed to a nucleophilic attack in the occupied oxo p orbital around the * orbital of the phosphite ester. From a fragment analysis, at the transition state, there is about 1.5 phosphite ester * character mixed in to the occupied valence orbitals. This mixing is only observed about the transition state, and may be eliminated by decreasing the O(Me)-P-O(Mo) angle. This benefits in an 4 kcal/mol energy penalty. Alternatively, there is 17 of your phosphite ester lone pair orbital mixed in to the unoccupied valence d orbital in the transition state (Figure 5B LUMO). Therefore, theFigure six. Mayer bond order (MBO) (A) and Mulliken charge alter (B) for reaction 1 along the reaction coordinate when it comes to Mo-O distance. Spec MoO indicating the spectator oxo in [MoVIO2(mnt)2]2-, that is the oxo atom that may be not transferred. The dashed line indicates the distance in TS3.of Mayer bond orders at the transition state: 1/3 of the Mo- O bond order is lost (a decrease in MBO from 1.84 to 1.17) and 1/4 of your P-O bond is formed (an increase from 0.00 to 0.43; the MBO for the PO bond in the solution is 1.80). Figure 6B shows that about 1/3 of the charge has been transferred from the substrate for the Mo complicated at this transition state. The above final results indicate that this oxo transfer reaction has an early transition state, with only 0.1 ?of Mo-O bond elongation. The calculations show that there is not a great deal structural rearrangement with the dithiolenes along with the spectator oxo atom in this oxo transfer reaction. When this oxo transfer is complete,dx.doi.org/10.1021/ja503316p | J. Am. Chem. Soc. 2014, 136, 9094-Journal in the American Chemical Society but together with the phosphate ester solution nevertheless bound (P in Figure 5A, which was obtained from a point around the IRC toward the product having a Mo-O(phosphite ester) bond distance of 2.Formula of 154012-18-7 24 ?, the two dithiolene planes stay perpendicular to every single other, as in R and TS3.Buy1217500-64-5 However, P isn’t a regional minimum, as well as the solution is lost along the reaction coordinate to offer the monooxo MoIV complex.PMID:24360118 As the phosphate ester comes off, the two dithiolenes rotate into the exact same plane to kind P (Figure 5A), as well as the enthalpy is lowered by 25 kcal/mol from P to P. This really is in contrast towards the reaction coordinate in refs 18 and 20, where the item remained bound. This distinction reflects the fact that the final solution in reaction 1 is actually a five-coordinate [MoIVO(mnt)2]2- complicated which has its two dithiolenes coplanar. The 4 S p orbitals that are perpendicular to the dithiolene planes are parallel with each other, and this stabilizes the square pyramidal five-coordinate Mo monooxo complex. 3.three.two. Transf.
