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Calculated by using B3LYP/SDD, with the same functional and basis as for the metal-containing molecules studied in this paper
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(a) Calculated by using B3LYP/SDD, with the same functional and basis as for the metal-containing molecules studied in this paper.
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To be published soon.
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To be published soon.
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An angular parameter τ maybe used to classify the geometry of pentacoordinate compounds. It is defined as τ, α- β)/60, where α and β are the two largest L-M-L angles, and α ≥ β. A perfect trigonal bipyramid has α, 180° and β, 120°, thus τ, 1, whereas in a perfect square pyramid α, β, i.e, τ, 0, a Addison, A. W, Rao, T. N, Reedijk, J, Rijn, v. J, Verschoor, G. C. J. Chem. Soc. Dalton. Trans. 1984, 1349-1356
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An angular parameter τ maybe used to classify the geometry of pentacoordinate compounds. It is defined as τ = (α- β)/60, where α and β are the two largest L-M-L angles, and α ≥ β. A perfect trigonal bipyramid has α = 180° and β = 120°, thus τ = 1, whereas in a perfect square pyramid α = β, i.e., τ = 0. (a) Addison, A. W.; Rao, T. N.; Reedijk, J.; Rijn, v. J.; Verschoor, G. C. J. Chem. Soc. Dalton. Trans. 1984, 1349-1356.
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34247140189
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2〉 values corresponding to singlet and triplet of 15′ are 0.13 and 2.02, respectively.
-
2〉 values corresponding to singlet and triplet of 15′ are 0.13 and 2.02, respectively.
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49
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34247096057
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Details can be found in the Supporting Information
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Details can be found in the Supporting Information.
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The potential energy surfaces for the rearrangement of osmaenediyne 6 computed with BLYP/SDD, B3LYP/LANL2DZ, and BLYP/LANL2DZ are reported in the Supporting Information.
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The potential energy surfaces for the rearrangement of osmaenediyne 6 computed with BLYP/SDD, B3LYP/LANL2DZ, and BLYP/LANL2DZ are reported in the Supporting Information.
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34247104923
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These orbitals are those expected for a restricted HF solution. The actual α and β spin orbitals in an unrestricted HF calculations are localized on one or the other p-benzyne carbon. This is not true for the HOMO of 8, where the UB3LYP calculations yield orbitals identical for α and β spins (shown in Figure 7).
-
These orbitals are those expected for a restricted HF solution. The actual α and β spin orbitals in an unrestricted HF calculations are localized on one or the other p-benzyne carbon. This is not true for the HOMO of 8, where the UB3LYP calculations yield orbitals identical for α and β spins (shown in Figure 7).
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34247156203
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2〉 of singlet (from triplet geometry) and triplet are provided in the Supporting Information.
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2〉 of singlet (from triplet geometry) and triplet are provided in the Supporting Information.
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34247113259
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Note again, as we discussed in the text around structure 8, that we avoid a discussion of the bond order of the various bonds but do give their computed lengths.
-
Note again, as we discussed in the text around structure 8, that we avoid a discussion of the bond order of the various bonds but do give their computed lengths.
-
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66
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34247160866
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The HOMO and LUMO of singlet 8, 8′, 11, 11′, and 15 are shown in the Supporting Information.
-
The HOMO and LUMO of singlet 8, 8′, 11, 11′, and 15 are shown in the Supporting Information.
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67
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34247128693
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Eight potential isomers arising in the Berry pseudorotation of 13 were optimized. Two trigonal bipyramids and two square pyramids collapsed to complex 13 ([0] kcal/mol). Three other isomers (including one trigonal bipyramid and two square pyramids) transformed into a trigonal bipyramidal structure 7 kcal/mol less stable than 13. One optimized trigonal bipyramid was +11 kcal higher in energy than 13.
-
Eight potential isomers arising in the Berry pseudorotation of 13 were optimized. Two trigonal bipyramids and two square pyramids collapsed to complex 13 ([0] kcal/mol). Three other isomers (including one trigonal bipyramid and two square pyramids) transformed into a trigonal bipyramidal structure 7 kcal/mol less stable than 13. One optimized trigonal bipyramid was +11 kcal higher in energy than 13.
-
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34247154856
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The reaction energies for the hydrogenation of metallabenzynes 8, 11, and 15 are given in the Supporting Information.
-
The reaction energies for the hydrogenation of metallabenzynes 8, 11, and 15 are given in the Supporting Information.
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