Online Demo Results
| Specifier | Space group |
|---|---|
| Extraction Method | AutoTableParser |
| Specifier Updated | False |
| Specifier | Crystal system |
|---|---|
| System | triclinic |
| Value | 1218.2 |
|---|---|
| Units | Angstrom^(3.0) |
| Raw Value | 1218.2(1) |
| Raw Units | Å3 |
| Specifier | V |
| error | 0.1 |
| Symbol | P1̄ |
|---|---|
| Specifier | Space group |
| Value | 9.8872 |
|---|---|
| Units | Angstrom^(1.0) |
| Raw Value | 9.8872(5) |
| Raw Units | Å |
| Specifier | a |
| error | 0.0005 |
| Value | 9.9387 |
|---|---|
| Units | Angstrom^(1.0) |
| Raw Value | 9.9387(5) |
| Raw Units | Å |
| Specifier | b |
| error | 0.0005 |
| Value | 12.7418 |
|---|---|
| Units | Angstrom^(1.0) |
| Raw Value | 12.7418(6) |
| Raw Units | Å |
| Specifier | c |
| error | 0.0006000000000000001 |
| Value | 86.26 |
|---|---|
| Units | Degrees^(1.0) |
| Raw Value | 86.260(3) |
| Raw Units | ° |
| Specifier | β |
| error | 0.003 |
| Value | 77.79 |
|---|---|
| Units | Degrees^(1.0) |
| Raw Value | 77.790(3) |
| Raw Units | ° |
| Specifier | α |
| error | 0.003 |
| Value | 85.324 |
|---|---|
| Units | Degrees^(1.0) |
| Raw Value | 85.324(3) |
| Raw Units | ° |
| Specifier | γ |
| error | 0.003 |
| Specifier | Space group |
|---|
| Value | 2.0 |
|---|---|
| Raw Value | 2 |
| Specifier | Z |
| Value | 624.0 |
|---|---|
| Raw Value | 624.00 |
| Specifier | F(000) |
| Value | 183.2 |
|---|---|
| Units | Kelvin^(1.0) |
| Raw Value | 183.2 |
| Raw Units | K |
| Specifier | T |
| Value | 0.845 |
|---|---|
| Units | (10^3.0) * Meter^(-1.0) |
| Raw Value | 0.845 |
| Raw Units | mm−1 |
| Specifier | μ(Mo-Kα) |
| Value | 626.44 |
|---|---|
| Raw Value | 626.44 |
| Specifier | Formula weight |
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Table 1 Data on the fluxionality
| Data | Row Categories | Column Categories |
|---|---|---|
| [{CCC}PdBr] | 1 | Complex |
| 350 | 1 | T(coal.)/K |
| 70.9 | 1 | ΔG†/kJ mol−1 |
| d6-dmso | 1 | Solvent |
| [{CNC}PdCl]Cl | 2 | Complex |
| 308 | 2 | T(coal.)/K |
| 59.3 | 2 | ΔG†/kJ mol−1 |
| CDCl3 | 2 | Solvent |
| [{CNC}PdCl]OTs | 3 | Complex |
| 343 | 3 | T(coal.)/K |
| 66.0 | 3 | ΔG†/kJ mol−1 |
| d6-dmso | 3 | Solvent |
| [{CNC}PdBr]Br | 4 | Complex |
| 278 | 4 | T(coal.)/K |
| 52.9 | 4 | ΔG†/kJ mol−1 |
| CDCl3 | 4 | Solvent |
| [{CNC}PdBr]OTs | 5 | Complex |
| 373 | 5 | T(coal.)/K |
| 77.6 | 5 | ΔG†/kJ mol−1 |
| d6-dmso | 5 | Solvent |
| [{CNC}PdI]I | 6 | Complex |
| 208 | 6 | T(coal.)/K |
| 41.9 | 6 | ΔG†/kJ mol−1 |
| CD2Cl2 | 6 | Solvent |
| [{CNC}PdI]OTs | 7 | Complex |
| 338 | 7 | T(coal.)/K |
| 70.9 | 7 | ΔG†/kJ mol−1 |
| d6-dmso | 7 | Solvent |
| [{CNC}Pd(OH2)][BF4]2 | 8 | Complex |
| >353 | 8 | T(coal.)/K |
| >73 | 8 | ΔG†/kJ mol−1 |
| CDCl3 | 8 | Solvent |
| [{CNC}PdCl]Cl | 9 | Complex |
| 303 | 9 | T(coal.)/K |
| 60.0 | 9 | ΔG†/kJ mol−1 |
| CD2Cl2 | 9 | Solvent |
| [{CNC}Pd(py)][BF4]2 | 10 | Complex |
| >403 | 10 | T(coal.)/K |
| >73 | 10 | ΔG†/kJ mol−1 |
| d6-dmso | 10 | Solvent |
| [{CNC′}PdBr]Br | 11 | Complex |
| 303 | 11 | T(coal.)/K |
| 57.4 | 11 | ΔG†/kJ mol−1 |
| CDCl3 | 11 | Solvent |
| [{CNC}Pd(OH2)][BF4]2 | 12 | Complex |
| 343 | 12 | T(coal.)/K |
| 68.5 | 12 | ΔG†/kJ mol−1 |
| d6-dmso | 12 | Solvent |
Table 2 Selected bond lengths and angles for complex [{CNC}Pd(C5H4N)][BF4]2
| Data | Row Categories | Column Categories |
|---|---|---|
| 2.060(4) | Pd(1)–N(5) | Bond lengths/Å |
| 2.017(4) | Pd(1)–N(6) | Bond lengths/Å |
| 2.021(4) | Pd(1)–C(11) | Bond lengths/Å |
| 2.027(4) | Pd(1)–C(21) | Bond lengths/Å |
| Bond angles/deg. | Bond angles/deg. | Bond lengths/Å |
| 87.8(2) | N(5)–Pd(1)–C(11) | Bond lengths/Å |
| 88.4(2) | N(5)–Pd(1)–C(21) | Bond lengths/Å |
| 92.1(2) | N(6)–Pd(1)–C(11) | Bond lengths/Å |
| 91.8(2) | N(6)–Pd(1)–C(21) | Bond lengths/Å |
| 178.5(2) | N(5)–Pd(1)–N(6) | Bond lengths/Å |
| 175.6(2) | C(11)–Pd(1)–C(21) | Bond lengths/Å |
| Dihedral angles/deg. | Dihedral angles/deg. | Bond lengths/Å |
| −41.1(3) | C(11)–Pd(1)–N(5)–C(1) | Bond lengths/Å |
| −65.1(3) | C(11)–Pd(1)–N(6)–C(1) | Bond lengths/Å |
| 40.4(4) | N(6)–Pd(1)–C(11)–N(2) | Bond lengths/Å |
| 39.2(5) | N(6)–Pd(1)–C(21)–N(4) | Bond lengths/Å |
Table 3 Crystal data and structure refinement for [{CNC}Pd(C5H4N)][BF4]2
| Data | Row Categories | Column Categories |
|---|---|---|
| 626.44 | Formula weight | C20H22B2F8N6Pd |
| 0.07 × 0.07 × 0.12 | Crystal dimensions/mm | C20H22B2F8N6Pd |
| triclinic | Crystal system | C20H22B2F8N6Pd |
| P1̄ | Space group | C20H22B2F8N6Pd |
| 9.8872(5) | a/Å | C20H22B2F8N6Pd |
| 9.9387(5) | b/Å | C20H22B2F8N6Pd |
| 12.7418(6) | c/Å | C20H22B2F8N6Pd |
| 77.790(3) | α/° | C20H22B2F8N6Pd |
| 86.260(3) | β/° | C20H22B2F8N6Pd |
| 85.324(3) | γ/° | C20H22B2F8N6Pd |
| 1218.2(1) | V/Å3 | C20H22B2F8N6Pd |
| 2 | Z | C20H22B2F8N6Pd |
| 624.00 | F(000) | C20H22B2F8N6Pd |
| 183.2 | T/K | C20H22B2F8N6Pd |
| 1.708 | Dc/Mg m−3 | C20H22B2F8N6Pd |
| 0.845 | μ(Mo-Kα)/mm−1 | C20H22B2F8N6Pd |
| 15462 | No. collected reflections | C20H22B2F8N6Pd |
| 5578, 0.047 | No. unique reflections, Rint | C20H22B2F8N6Pd |
| 3701 | No. of observed reflections | C20H22B2F8N6Pd |
| 334 | No. of refined parameters | C20H22B2F8N6Pd |
| 0.049 | wR(F) | C20H22B2F8N6Pd |
| 0.041 | R[I > 3σ(I)] | C20H22B2F8N6Pd |
| 1.18 | Goodness-of-fit | C20H22B2F8N6Pd |
| 0.92, −0.50 | (Δρ) max, min/e Å−3 | C20H22B2F8N6Pd |
Table 4 Comparison of experimental bond distances and angles for Pd{CEC}Br, 1 (E = C), and [Pd{CEC}Br][Br], 2 (E = N), with that of the calculated complexes Pd{CEC}Br, GS(1Br) (E = C), and Pd{CEC}Br+,GS(2Br) (E = N)
| Data | Row Categories | Column Categories |
|---|---|---|
| Bond lengths/Å | Bond lengths/Å | 1 |
| Bond lengths/Å | Bond lengths/Å | GS(1Br) |
| Bond lengths/Å | Bond lengths/Å | 2 |
| Bond lengths/Å | Bond lengths/Å | GS(2Br) |
| 2.014 | Pd–E | 1 |
| 2.017 | Pd–E | GS(1Br) |
| 2.066 | Pd–E | 2 |
| 2.093 | Pd–E | GS(2Br) |
| 2.00 | Pd–C(11) | 1 |
| 2.035 | Pd–C(11) | GS(1Br) |
| 2.020 | Pd–C(11) | 2 |
| 2.034 | Pd–C(11) | GS(2Br) |
| 2.5388 | Pd–Br | 1 |
| 2.558 | Pd–Br | GS(1Br) |
| 2.4250 | Pd–Br | 2 |
| 2.422 | Pd–Br | GS(2Br) |
| 1.33 | C(12)–C(13) | 1 |
| 1.366 | C(12)–C(13) | GS(1Br) |
| 1.328 | C(12)–C(13) | 2 |
| 1.358 | C(12)–C(13) | GS(2Br) |
| Bond angles/deg. | Bond angles/deg. | 1 |
| Bond angles/deg. | Bond angles/deg. | GS(1Br) |
| Bond angles/deg. | Bond angles/deg. | 2 |
| Bond angles/deg. | Bond angles/deg. | GS(2Br) |
| 170.9 | C(11)–Pd–C(21) | 1 |
| 172.2 | C(11)–Pd–C(21) | GS(1Br) |
| 173.2 | C(11)–Pd–C(21) | 2 |
| 174.9 | C(11)–Pd–C(21) | GS(2Br) |
| 85.1 | E–Pd–C(11) | 1 |
| 86.1 | E–Pd–C(11) | GS(1Br) |
| 86.7 | E–Pd–C(11) | 2 |
| 87.5 | E–Pd–C(11) | GS(2Br) |
| 179.6 | E–Pd–Br | 1 |
| 180.0 | E–Pd–Br | GS(1Br) |
| 178.9 | E–Pd–Br | 2 |
| 180.0 | E–Pd–Br | GS(2Br) |
| Dihedral angles/deg. | Dihedral angles/deg. | 1 |
| Dihedral angles/deg. | Dihedral angles/deg. | GS(1Br) |
| Dihedral angles/deg. | Dihedral angles/deg. | 2 |
| Dihedral angles/deg. | Dihedral angles/deg. | GS(2Br) |
| 42.9 | C(1)–E–Pd–C(11) | 1 |
| 41.3 | C(1)–E–Pd–C(11) | GS(1Br) |
| 40.6 | C(1)–E–Pd–C(11) | 2 |
| 41.0 | C(1)–E–Pd–C(11) | GS(2Br) |
| 49.3 | N(1)–C(7)–C(1)–C(6) | 1 |
| 52.7 | N(1)–C(7)–C(1)–C(6) | GS(1Br) |
| 57.2 | N(1)–C(7)–C(1)–C(6) | 2 |
| 56.3 | N(1)–C(7)–C(1)–C(6) | GS(2Br) |
| 95.4 | N(2)–C(11)–C(21)–N(4) | 1 |
| 96.8 | N(2)–C(11)–C(21)–N(4) | GS(1Br) |
| 101.3 | N(2)–C(11)–C(21)–N(4) | 2 |
| 91.8 | N(2)–C(11)–C(21)–N(4) | GS(2Br) |
Table 5 Selected bond distance (Å), angles and dihedral angles (degrees) for the calculated complexes involved in the two-step fluxional process for [{CCC}PdX] and [{CNC}PdX]+ (X = Cl, Br, I)
| Data | Row Categories | Column Categories |
|---|---|---|
| 2.428 | Pd–X | X = Cl , GS(1Cl) |
| 2.449 | Pd–X | X = Cl , TS(1Cl) |
| 2.445 | Pd–X | X = Cl , Int(1Cl) |
| 2.558 | Pd–X | X = Br , GS(1Br) |
| 2.595 | Pd–X | X = Br , TS(1Br) |
| 2.581 | Pd–X | X = Br , Int(1Br) |
| 2.742 | Pd–X | X = I , GS(1I) |
| 2.783 | Pd–X | X = I , TS(1I) |
| 2.774 | Pd–X | X = I , Int(1I) |
| 2.015 | Pd–C(6) | X = Cl , GS(1Cl) |
| 2.048 | Pd–C(6) | X = Cl , TS(1Cl) |
| 2.055 | Pd–C(6) | X = Cl , Int(1Cl) |
| 2.018 | Pd–C(6) | X = Br , GS(1Br) |
| 2.049 | Pd–C(6) | X = Br , TS(1Br) |
| 2.060 | Pd–C(6) | X = Br , Int(1Br) |
| 2.020 | Pd–C(6) | X = I , GS(1I) |
| 2.056 | Pd–C(6) | X = I , TS(1I) |
| 2.065 | Pd–C(6) | X = I , Int(1I) |
| 2.034 | Pd–C(11) | X = Cl , GS(1Cl) |
| 2.016 | Pd–C(11) | X = Cl , TS(1Cl) |
| 2.042 | Pd–C(11) | X = Cl , Int(1Cl) |
| 2.035 | Pd–C(11) | X = Br , GS(1Br) |
| 2.012 | Pd–C(11) | X = Br , TS(1Br) |
| 2.037 | Pd–C(11) | X = Br , Int(1Br) |
| 2.034 | Pd–C(11) | X = I , GS(1I) |
| 2.015 | Pd–C(11) | X = I , TS(1I) |
| 2.034 | Pd–C(11) | X = I , Int(1I) |
| 2.034 | Pd–C(21) | X = Cl , GS(1Cl) |
| 2.067 | Pd–C(21) | X = Cl , TS(1Cl) |
| 2.042 | Pd–C(21) | X = Cl , Int(1Cl) |
| 2.035 | Pd–C(21) | X = Br , GS(1Br) |
| 2.067 | Pd–C(21) | X = Br , TS(1Br) |
| 2.040 | Pd–C(21) | X = Br , Int(1Br) |
| 2.034 | Pd–C(21) | X = I , GS(1I) |
| 2.055 | Pd–C(21) | X = I , TS(1I) |
| 2.034 | Pd–C(21) | X = I , Int(1I) |
| 180.0 | C(6)–Pd–X | X = Cl , GS(1Cl) |
| 158.9 | C(6)–Pd–X | X = Cl , TS(1Cl) |
| 159.4 | C(6)–Pd–X | X = Cl , Int(1Cl) |
| 180.0 | C(6)–Pd–X | X = Br , GS(1Br) |
| 154.9 | C(6)–Pd–X | X = Br , TS(1Br) |
| 156.2 | C(6)–Pd–X | X = Br , Int(1Br) |
| 180.0 | C(6)–Pd–X | X = I , GS(1I) |
| 151.6 | C(6)–Pd–X | X = I , TS(1I) |
| 151.6 | C(6)–Pd–X | X = I , Int(1I) |
| 173.2 | C(11)–Pd–C(21) | X = Cl , GS(1Cl) |
| 159.6 | C(11)–Pd–C(21) | X = Cl , TS(1Cl) |
| 157.3 | C(11)–Pd–C(21) | X = Cl , Int(1Cl) |
| 172.2 | C(11)–Pd–C(21) | X = Br , GS(1Br) |
| 159.6 | C(11)–Pd–C(21) | X = Br , TS(1Br) |
| 156.5 | C(11)–Pd–C(21) | X = Br , Int(1Br) |
| 171.5 | C(11)–Pd–C(21) | X = I , GS(1I) |
| 158.7 | C(11)–Pd–C(21) | X = I , TS(1I) |
| 156.0 | C(11)–Pd–C(21) | X = I , Int(1I) |
| −52.2 | C(6)–C(1)–C(7)–N(1) | X = Cl , GS(1Cl) |
| −54.8 | C(6)–C(1)–C(7)–N(1) | X = Cl , TS(1Cl) |
| −49.6 | C(6)–C(1)–C(7)–N(1) | X = Cl , Int(1Cl) |
| −52.7 | C(6)–C(1)–C(7)–N(1) | X = Br , GS(1Br) |
| −54.9 | C(6)–C(1)–C(7)–N(1) | X = Br , TS(1Br) |
| −50.5 | C(6)–C(1)–C(7)–N(1) | X = Br , Int(1Br) |
| −52.9 | C(6)–C(1)–C(7)–N(1) | X = I , GS(1I) |
| −55.1 | C(6)–C(1)–C(7)–N(1) | X = I , TS(1I) |
| −49.2 | C(6)–C(1)–C(7)–N(1) | X = I , Int(1I) |
| −52.2 | C(6)–C(5)–C(8)–N(3) | X = Cl , GS(1Cl) |
| 33.2 | C(6)–C(5)–C(8)–N(3) | X = Cl , TS(1Cl) |
| 49.7 | C(6)–C(5)–C(8)–N(3) | X = Cl , Int(1Cl) |
| −52.7 | C(6)–C(5)–C(8)–N(3) | X = Br , GS(1Br) |
| 27.6 | C(6)–C(5)–C(8)–N(3) | X = Br , TS(1Br) |
| 49.1 | C(6)–C(5)–C(8)–N(3) | X = Br , Int(1Br) |
| −52.9 | C(6)–C(5)–C(8)–N(3) | X = I , GS(1I) |
| 27.2 | C(6)–C(5)–C(8)–N(3) | X = I , TS(1I) |
| 49.2 | C(6)–C(5)–C(8)–N(3) | X = I , Int(1I) |
| Data | Row Categories | Column Categories |
|---|---|---|
| 2.294 | Pd–X | GS(2Cl) |
| 2.300 | Pd–X | TS(2Cl) |
| 2.308 | Pd–X | Int(2Cl) |
| 2.422 | Pd–X | GS(2Br) |
| 2.436 | Pd–X | TS(2Br) |
| 2.437 | Pd–X | Int(2Br) |
| 2.607 | Pd–X | GS(2I) |
| 2.630 | Pd–X | TS(2I) |
| 2.626 | Pd–X | Int(2I) |
| 2.081 | Pd–N(5) | GS(2Cl) |
| 2.159 | Pd–N(5) | TS(2Cl) |
| 2.174 | Pd–N(5) | Int(2Cl) |
| 2.093 | Pd–N(5) | GS(2Br) |
| 2.167 | Pd–N(5) | TS(2Br) |
| 2.193 | Pd–N(5) | Int(2Br) |
| 2.104 | Pd–N(5) | GS(2I) |
| 2.182 | Pd–N(5) | TS(2I) |
| 2.226 | Pd–N(5) | Int(2I) |
| 2.031 | Pd–C(11) | GS(2Cl) |
| 2.029 | Pd–C(11) | TS(2Cl) |
| 2.046 | Pd–C(11) | Int(2Cl) |
| 2.034 | Pd–C(11) | GS(2Br) |
| 2.021 | Pd–C(11) | TS(2Br) |
| 2.046 | Pd–C(11) | Int(2Br) |
| 2.037 | Pd–C(11) | GS(2I) |
| 2.013 | Pd–C(11) | TS(2I) |
| 2.035 | Pd–C(11) | Int(2I) |
| 2.031 | Pd–C(21) | GS(2Cl) |
| 2.064 | Pd–C(21) | TS(2Cl) |
| 2.046 | Pd–C(21) | Int(2Cl) |
| 2.034 | Pd–C(21) | GS(2Br) |
| 2.068 | Pd–C(21) | TS(2Br) |
| 2.037 | Pd–C(21) | Int(2Br) |
| 2.037 | Pd–C(21) | GS(2I) |
| 2.067 | Pd–C(21) | TS(2I) |
| 2.035 | Pd–C(21) | Int(2I) |
| 180.0 | N(5)–Pd-X | GS(2Cl) |
| 162.3 | N(5)–Pd-X | TS(2Cl) |
| 158.6 | N(5)–Pd-X | Int(2Cl) |
| 180.0 | N(5)–Pd-X | GS(2Br) |
| 158.8 | N(5)–Pd-X | TS(2Br) |
| 155.1 | N(5)–Pd-X | Int(2Br) |
| 180.0 | N(5)–Pd-X | GS(2I) |
| 153.5 | N(5)–Pd-X | TS(2I) |
| 147.9 | N(5)–Pd-X | Int(2I) |
| 175.8 | C(11)–Pd–C(21) | GS(2Cl) |
| 163.6 | C(11)–Pd–C(21) | TS(2Cl) |
| 161.0 | C(11)–Pd–C(21) | Int(2Cl) |
| 174.9 | C(11)–Pd–C(21) | GS(2Br) |
| 163.8 | C(11)–Pd–C(21) | TS(2Br) |
| 161.1 | C(11)–Pd–C(21) | Int(2Br) |
| 173.8 | C(11)–Pd–C(21) | GS(2I) |
| 164.1 | C(11)–Pd–C(21) | TS(2I) |
| 160.8 | C(11)–Pd–C(21) | Int(2I) |
| −55.9 | N(5)–C(1)–C(7)–N(1) | GS(2Cl) |
| −66.5 | N(5)–C(1)–C(7)–N(1) | TS(2Cl) |
| −61.3 | N(5)–C(1)–C(7)–N(1) | Int(2Cl) |
| −56.4 | N(5)–C(1)–C(7)–N(1) | GS(2Br) |
| −67.2 | N(5)–C(1)–C(7)–N(1) | TS(2Br) |
| −61.2 | N(5)–C(1)–C(7)–N(1) | Int(2Br) |
| −56.9 | N(5)–C(1)–C(7)–N(1) | GS(2I) |
| −66.4 | N(5)–C(1)–C(7)–N(1) | TS(2I) |
| −60.9 | N(5)–C(1)–C(7)–N(1) | Int(2I) |
| −55.9 | N(5)–C(5)–C(8)–N(3) | GS(2Cl) |
| 50.9 | N(5)–C(5)–C(8)–N(3) | TS(2Cl) |
| 61.3 | N(5)–C(5)–C(8)–N(3) | Int(2Cl) |
| −56.4 | N(5)–C(5)–C(8)–N(3) | GS(2Br) |
| 43.6 | N(5)–C(5)–C(8)–N(3) | TS(2Br) |
| 61.7 | N(5)–C(5)–C(8)–N(3) | Int(2Br) |
| −56.9 | N(5)–C(5)–C(8)–N(3) | GS(2I) |
| 33.2 | N(5)–C(5)–C(8)–N(3) | TS(2I) |
| 60.9 | N(5)–C(5)–C(8)–N(3) | Int(2I) |
Table 6 Activation energy and relative energy (kJ mol−1) of the intermediate for the two-step fluxional process for [{CCC}PdX] and [{CNC}PdX]+ (X = Cl, Br, I). See Scheme 1 for definition of ΔE† and ΔE. GP stands for Gas Phase calculations at the B3PW91 model and PCM corresponds to calculations with a continuum model for the solvent on the B3PW91 optimized geometries
| Data | Row Categories | Column Categories |
|---|---|---|
| 69.9 | X = Cl | [{CCC}PdX] , ΔE† , GP |
| 69.5 | X = Cl | [{CCC}PdX] , ΔE† , PCM |
| 68.0 | X = Cl | [{CCC}PdX] , ΔE , GP |
| 68.9 | X = Cl | [{CCC}PdX] , ΔE , PCM |
| 73.2 | X = Cl | [{CNC}PdX]+ , ΔE† , GP |
| 75.5 | X = Cl | [{CNC}PdX]+ , ΔE† , PCM |
| 74.9 | X = Cl | [{CNC}PdX]+ , ΔE , GP |
| 71.8 | X = Cl | [{CNC}PdX]+ , ΔE , PCM |
| 71.4 | X = Br | [{CCC}PdX] , ΔE† , GP |
| 72.3 | X = Br | [{CCC}PdX] , ΔE† , PCM |
| 68.2 | X = Br | [{CCC}PdX] , ΔE , GP |
| 71.2 | X = Br | [{CCC}PdX] , ΔE , PCM |
| 73.0 | X = Br | [{CNC}PdX]+ , ΔE† , GP |
| 75.3 | X = Br | [{CNC}PdX]+ , ΔE† , PCM |
| 72.3 | X = Br | [{CNC}PdX]+ , ΔE , GP |
| 66.6 | X = Br | [{CNC}PdX]+ , ΔE , PCM |
| 72.5 | X = I | [{CCC}PdX] , ΔE† , GP |
| 72.4 | X = I | [{CCC}PdX] , ΔE† , PCM |
| 69.0 | X = I | [{CCC}PdX] , ΔE , GP |
| 66.5 | X = I | [{CCC}PdX] , ΔE , PCM |
| 72.9 | X = I | [{CNC}PdX]+ , ΔE† , GP |
| 79.3 | X = I | [{CNC}PdX]+ , ΔE† , PCM |
| 69.7 | X = I | [{CNC}PdX]+ , ΔE , GP |
| 67.2 | X = I | [{CNC}PdX]+ , ΔE , PCM |
Table 7 Selected bond distance (Å), angles and dihedral angles (degrees) for the calculated complexes involved in the two-step fluxional process for [{CNC}PdX2] (X = Cl, Br, I)
| Data | Row Categories | Column Categories |
|---|---|---|
| 2.390 | Pd–X | X = Cl , GS(2Cl2) |
| 2.367 | Pd–X | X = Cl , TS(2Cl2) |
| 2.370 | Pd–X | X = Cl , Int(2Cl2) |
| 2.531 | Pd–X | X = Br , GS(2Br2) |
| 2.503 | Pd–X | X = Br , TS(2Br2) |
| 2.505 | Pd–X | X = Br , Int(2Br2) |
| 2.730 | Pd–X | X = I , GS(2I2) |
| 2.695 | Pd–X | X = I , TS(2I2) |
| 2.695 | Pd–X | X = I , Int(2I2) |
| 2.578 | Pd–N(5) | X = Cl , GS(2Cl2) |
| 2.657 | Pd–N(5) | X = Cl , TS(2Cl2) |
| 2.753 | Pd–N(5) | X = Cl , Int(2Cl2) |
| 2.554 | Pd–N(5) | X = Br , GS(2Br2) |
| 2.635 | Pd–N(5) | X = Br , TS(2Br2) |
| 2.735 | Pd–N(5) | X = Br , Int(2Br2) |
| 2.525 | Pd–N(5) | X = I , GS(2I2) |
| 2.605 | Pd–N(5) | X = I , TS(2I2) |
| 2.713 | Pd–N(5) | X = I , Int(2I2) |
| 2.015 | Pd–C(11) | X = Cl , GS(2Cl2) |
| 2.016 | Pd–C(11) | X = Cl , TS(2Cl2) |
| 2.023 | Pd–C(11) | X = Cl , Int(2Cl2) |
| 2.015 | Pd–C(11) | X = Br , GS(2Br2) |
| 2.015 | Pd–C(11) | X = Br , TS(2Br2) |
| 2.021 | Pd–C(11) | X = Br , Int(2Br2) |
| 2.017 | Pd–C(11) | X = I , GS(2I2) |
| 2.016 | Pd–C(11) | X = I , TS(2I2) |
| 2.022 | Pd–C(11) | X = I , Int(2I2) |
| 2.023 | Pd–C(21) | X = Cl , GS(2Cl2) |
| 2.021 | Pd–C(21) | X = Cl , TS(2Cl2) |
| 2.022 | Pd–C(21) | X = Cl , Int(2Cl2) |
| 2.020 | Pd–C(21) | X = Br , GS(2Br2) |
| 2.020 | Pd–C(21) | X = Br , TS(2Br2) |
| 2.021 | Pd–C(21) | X = Br , Int(2Br2) |
| 2.018 | Pd–C(21) | X = I , GS(2I2) |
| 2.018 | Pd–C(21) | X = I , TS(2I2) |
| 2.022 | Pd–C(21) | X = I , Int(2I2) |
| 94.4 | N(5)–Pd–X | X = Cl , GS(2Cl2) |
| 93.9 | N(5)–Pd–X | X = Cl , TS(2Cl2) |
| 99.0 | N(5)–Pd–X | X = Cl , Int(2Cl2) |
| 96.3 | N(5)–Pd–X | X = Br , GS(2Br2) |
| 94.2 | N(5)–Pd–X | X = Br , TS(2Br2) |
| 99.3 | N(5)–Pd–X | X = Br , Int(2Br2) |
| 98.7 | N(5)–Pd–X | X = I , GS(2I2) |
| 94.9 | N(5)–Pd–X | X = I , TS(2I2) |
| 100.2 | N(5)–Pd–X | X = I , Int(2I2) |
| 85.4 | N(5)–Pd–C(11) | X = Cl , GS(2Cl2) |
| 90.7 | N(5)–Pd–C(11) | X = Cl , TS(2Cl2) |
| 88.1 | N(5)–Pd–C(11) | X = Cl , Int(2Cl2) |
| 85.3 | N(5)–Pd–C(11) | X = Br , GS(2Br2) |
| 90.5 | N(5)–Pd–C(11) | X = Br , TS(2Br2) |
| 88.3 | N(5)–Pd–C(11) | X = Br , Int(2Br2) |
| 86.0 | N(5)–Pd–C(11) | X = I , GS(2I2) |
| 90.5 | N(5)–Pd–C(11) | X = I , TS(2I2) |
| 88.5 | N(5)–Pd–C(11) | X = I , Int(2I2) |
| 168.6 | C(11)–Pd–C(21) | X = Cl , GS(2Cl2) |
| 172.0 | C(11)–Pd–C(21) | X = Cl , TS(2Cl2) |
| 175.4 | C(11)–Pd–C(21) | X = Cl , Int(2Cl2) |
| 169.9 | C(11)–Pd–C(21) | X = Br , GS(2Br2) |
| 172.3 | C(11)–Pd–C(21) | X = Br , TS(2Br2) |
| 176.1 | C(11)–Pd–C(21) | X = Br , Int(2Br2) |
| 171.9 | C(11)–Pd–C(21) | X = I , GS(2I2) |
| 173.2 | C(11)–Pd–C(21) | X = I , TS(2I2) |
| 176.5 | C(11)–Pd–C(21) | X = I , Int(2I2) |
| −63.1 | N(5)–C(1)–C(7)–N(1) | X = Cl , GS(2Cl2) |
| −94.4 | N(5)–C(1)–C(7)–N(1) | X = Cl , TS(2Cl2) |
| −93.1 | N(5)–C(1)–C(7)–N(1) | X = Cl , Int(2Cl2) |
| −56.9 | N(5)–C(1)–C(7)–N(1) | X = Br , GS(2Br2) |
| −91.3 | N(5)–C(1)–C(7)–N(1) | X = Br , TS(2Br2) |
| −92.3 | N(5)–C(1)–C(7)–N(1) | X = Br , Int(2Br2) |
| −53.2 | N(5)–C(1)–C(7)–N(1) | X = I , GS(2I2) |
| −87.4 | N(5)–C(1)–C(7)–N(1) | X = I , TS(2I2) |
| −90.7 | N(5)–C(1)–C(7)–N(1) | X = I , Int(2I2) |
| −47.0 | N(5)–C(5)–C(8)–N(3) | X = Cl , GS(2Cl2) |
| 31.1 | N(5)–C(5)–C(8)–N(3) | X = Cl , TS(2Cl2) |
| 93.2 | N(5)–C(5)–C(8)–N(3) | X = Cl , Int(2Cl2) |
| −51.6 | N(5)–C(5)–C(8)–N(3) | X = Br , GS(2Br2) |
| 24.8 | N(5)–C(5)–C(8)–N(3) | X = Br , TS(2Br2) |
| 92.3 | N(5)–C(5)–C(8)–N(3) | X = Br , Int(2Br2) |
| −53.0 | N(5)–C(5)–C(8)–N(3) | X = I , GS(2I2) |
| 19.2 | N(5)–C(5)–C(8)–N(3) | X = I , TS(2I2) |
| 90.7 | N(5)–C(5)–C(8)–N(3) | X = I , Int(2I2) |
Table 8 Activation energy and relative energy (kJ mol−1) of the intermediate for the two-step fluxional process [{CNC}PdX2] (X = Cl, Br, I). See Scheme 1 for definition of ΔE† and ΔE. GP stands for Gas Phase calculations at the B3PW91 model and PCM corresponds to calculation with a continuum model for the solvent on the B3PW91 optimized geometries
| Data | Row Categories | Column Categories |
|---|---|---|
| 11.2 | X = Cl | ΔE† , GP |
| 10.4 | X = Cl | ΔE† , PCM |
| 0.2 | X = Cl | ΔE , GP |
| 0.8 | X = Cl | ΔE , PCM |
| 10.3 | X = Br | ΔE† , GP |
| 11.9 | X = Br | ΔE† , PCM |
| −4.1 | X = Br | ΔE , GP |
| −1.4 | X = Br | ΔE , PCM |
| 10.1 | X = I | ΔE† , GP |
| 12.8 | X = I | ΔE† , PCM |
| −8.0 | X = I | ΔE , GP |
| −3.0 | X = I | ΔE , PCM |
Check out ImageDataExtractor to extract data from images.
Figure 2: Optimized geometry for Pd{CCC}Br, GS(1Br), and Pd{CNC}Br+, GS(2Br), at the B3PW91 level.
Copyright by Royal Society of Chemistry
Figure 3: Mechanism for interconversion for Pd{CCC}Br. Energies are in kJ mol−1.
Copyright by Royal Society of Chemistry
Figure 5: Mechanism for interconversion for Pd{CNC}2+. Energies are in kJ mol−1.
Copyright by Royal Society of Chemistry
Figure 6: Mechanism for interconversion for [Pd{CNC}(Br)2]. Energies are in kJ mol−1.
Copyright by Royal Society of Chemistry
| DOI | 10.1039/b210784h |
|---|---|
| Journal | Dalton Transactions |
| Volume | 0 |
| Issue | 5 |
| First Page | 831 |
| Last Page | 838 |
| Publisher | Royal Society of Chemistry |
| Published Date | 2003-02-24 |
| Authors | John R. Miecznikowski; Stephan Gründemann; Martin Albrecht; Claire Mégret; Eric Clot; Jack W. Faller; Odile Eisenstein; Robert H. Crabtree; John R. Miecznikowski; Stephan Gründemann; Martin Albrecht; Claire Mégret; Eric Clot; Jack W. Faller; Odile Eisenstein; Robert H. Crabtree |
| Title | Outer sphere anion participation can modify the mechanism for conformer interconversion in Pd pincer complexes |
| URL HTML | http://pubs.rsc.org/en/Content/ArticleLanding/2003/DT/B210784H |
| URL PDF | http://pubs.rsc.org/en/Content/ArticlePDF/2003/DT/B210784H |
Abbreviations
| CCC | ( η3-C,C′,C″ |
|---|---|
| CNC | (η3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine) |
| N(1) | −35.5(3) ° and N(5) – Pd(1) |
| C(1) | −41.1(3) ° and C(11) |
| PES | potential energy surface |
| RECP | relativistic effective core potential |
| DEPT | distortionless enhancement of polarization transfer |
| S-C-(CH)2 | S ) , 141.66 ( Cpara ) , 137.46 ( C-CH3 ) , 127.96 |
| S-C-(CH)2 | C-S ) , 141.78 ( Cpara ) , 137.64 ( C-CH3 ) , 128.09 |
| S-C-(CH)2 | S-C ) , 142.12 ( Cpara ) , 137.86 ( C-CH3 ) , 128.38 |
Quantity Definitions
| η3-C,C′,C″ | CCC = |
|---|---|
| (η3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine) | = |
| Table | pincer |
| Table | intermediate Int(1X) |
| ΔE | activation energy |
| ΔG | experiment |
| Table | activation energy |
| Table | TS |
| Table | energy pattern |
| TS(2□) | transition state |
| Table | experimental work |
| Tables | neutral ligand XIS |
| Table | CCC pincer |
| Table | bond distance |
| Table | I |
| Table | GS(2X2) |
| Table | energy pattern |
| α | f polarization function |
| α | polarization d function |
| Mo-Kα | Nonius KappaCCD |
| SORTAV | absorption |
| δ | NMR |
| δ | NMR |
| δ | NMR |
| δ | NMR |
| δ | NMR |
| δ | NMR |
| δ | NMR |
| δ | NMR |
| δ | NMR |
| δ | NMR |
Chemical Entity Mentions
| halide |
| acetone |
| C(21)–Pd–Br |
| Cortho |
| 1H |
| NCH2CH2CH2CH3 |
| CH3-C |
| Br |
| 1-butylimidazole |
| halides |
| N |
| imidazole |
| 2H |
| C(11)–Pd–C(21) |
| CNC |
| DMSO-d6 |
| Cl |
| pyridine |
| tridentate |
| (η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)chloropalladium(II)(1+) tosylate |
| CH2 |
| NCH3 |
| DMSO |
| CH2Cl2/pentane |
| tosylate |
| py-CH2-N |
| Pd |
| Et2O |
| CHCl3 |
| H3C-C-(CH)2 |
| 2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}phenyl |
| carbenes |
| 13C{1H} |
| [{CNC}Pd(C5H5N)][BF4]2 |
| CH3 |
| [{CNC}Pd(solvent)](BF4)2 |
| tosylate-H |
| 2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}phenyl)bromopalladium(II |
| (η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)aquapalladium(II)(2+) fluoroborate |
| Pd{CCC}Br |
| {CCC}Pd(XIS) |
| Pd–C(11) |
| C22H24N5IO3PdS·H2O |
| −20 °C |
| Pd{CNC}Br+ |
| pyCH2N |
| H |
| odile.eisenstein |
| C(6)–Pd–Br |
| diethyl ether |
| η3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine |
| aryl C(6) |
| AgOTs |
| iodide |
| SiMe4 |
| Celite |
| {CNC′}2 |
| (η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)bromopalladium(II)(1+) tosylate |
| Pd pincer |
| d6-dmso |
| EtOH |
| NaOTs |
| CH2Cl2 |
| methyl |
| CH2Cl2/Et2O |
| 2Br− |
| (η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)iodopalladium(II)(1+) iodide |
| NCHN |
| 4-coordinate |
| Pd{CEC}Br, GS(1Br) (E = C) |
| {CNC}PdX2 |
| bromide |
| [{CNC}PdCl]Cl |
| Pd(1)–N(5) |
| [{CNC}PdBr]Br |
| [{CNC}Pd(OH2)]+ |
| {CNC}Pd(XIS)][XOS |
| Pd(OAc)2 |
| methanol/Et2O |
| AgBF4 |
| C-CH3 |
| Pd–N(5) |
| Me |
| chloro |
| XOS |
| py-CH2N |
| 1,4-dioxane |
| pyridine N(5) |
| 2,6-bis(bromomethyl)pyridine |
| (η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)iodopalladium(II)(1+) tosylate |
| (η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)pyridinepalladium(II)(2+) fluoroborate |
| aryl |
| methanol |
| N-methyl |
| Pd{CEC}Br |
| acetone/Et2O |
| [{CNC}PdX]+ |
| Pd–C(11)–N(2) |
| Pd⋯C(14) |
| (η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)chloropalladium(II)(1+) chloride |
| CD2Cl2 |
| Hydrogen |
| Pd–C(6) |
| NCHHCH2CH2CH3 |
| hydrogen |
| GS(1Br) |
| Pd(II) |
| (η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)bromopalladium(II)(1+) bromide |
| carbene |
| [{CNC}Pd(C5H5N)](BF4)2 |
| 1-methylimidazole |
| N(4) |
| Iodide |
| Pd{CNC}2+ |
| n-Bu |
| Pd–Br |
| NaI |
| Cedex |
| palladium |
| CINES |
| R = Me |
| C15H17N5Cl2Pd1·1H2O |
| pyridine N |
| C22H24BrN5O3PdS·CH3OH |
| 2,6-bis(chloromethyl)pyridine |
| Pd–C(21) |
| [(CNC)Pd(py)](BF4)2 |
| C21H29Br2N5Pd |
| C(6) |
| NHCN |
| C(6)–Pd–C(21) |
| carbons |
| η3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)bromopalladium(II)(1+ |
| CH2 H |
| Pd{CNC}Br |
| chloride |
| (627.56)·0.5EtOH |
| methylene |
CDE v2 Output
[
{
"Document": {
"abbreviation_definitions": [
{
"abbreviation": "CCC",
"long_form": "( η3-C,C′,C″"
},
{
"abbreviation": "CNC",
"long_form": "(η3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)"
},
{
"abbreviation": "N(1)",
"long_form": "−35.5(3) ° and N(5) – Pd(1)"
},
{
"abbreviation": "C(1)",
"long_form": "−41.1(3) ° and C(11)"
},
{
"abbreviation": "PES",
"long_form": "potential energy surface"
},
{
"abbreviation": "RECP",
"long_form": "relativistic effective core potential"
},
{
"abbreviation": "DEPT",
"long_form": "distortionless enhancement of polarization transfer"
},
{
"abbreviation": "S-C-(CH)2",
"long_form": "S ) , 141.66 ( Cpara ) , 137.46 ( C-CH3 ) , 127.96"
},
{
"abbreviation": "S-C-(CH)2",
"long_form": "C-S ) , 141.78 ( Cpara ) , 137.64 ( C-CH3 ) , 128.09"
},
{
"abbreviation": "S-C-(CH)2",
"long_form": "S-C ) , 142.12 ( Cpara ) , 137.86 ( C-CH3 ) , 128.38"
}
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"units": "Kelvin^(1.0)",
"value": [
183.2
]
}
},
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"specifier": "Crystal system",
"structure_factor": {
"F": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"raw_value": "624.00",
"specifier": "F(000)",
"value": [
624.0
]
}
},
"z": {
"Z": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"raw_value": "2",
"specifier": "Z",
"value": [
2.0
]
}
}
}
},
"formula_weight_no_dim": {
"FormulaWeightNoDim": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"raw_value": "626.44",
"specifier": "Formula weight",
"value": [
626.44
]
}
},
"specifier": "system"
}
},
{
"Crystal": {
"cde2_method": "AutoTableParser",
"cde2_updated": false,
"cell_params": {
"UnitCell": {
"cell_volume": {
"CellVolume": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"error": 0.1,
"raw_units": "Å3",
"raw_value": "1218.2(1)",
"specifier": "V",
"units": "Angstrom^(3.0)",
"value": [
1218.2
]
}
},
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"lattice_param_a": {
"CellLengthA": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"error": 0.0005,
"raw_units": "Å",
"raw_value": "9.8872(5)",
"specifier": "a",
"units": "Angstrom^(1.0)",
"value": [
9.8872
]
}
},
"lattice_param_alpha": {
"CellAngleAlpha": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"error": 0.003,
"raw_units": "°",
"raw_value": "77.790(3)",
"specifier": "α",
"units": "Degrees^(1.0)",
"value": [
77.79
]
}
},
"lattice_param_b": {
"CellLengthB": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"error": 0.0005,
"raw_units": "Å",
"raw_value": "9.9387(5)",
"specifier": "b",
"units": "Angstrom^(1.0)",
"value": [
9.9387
]
}
},
"lattice_param_beta": {
"CellAngleBeta": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"error": 0.003,
"raw_units": "°",
"raw_value": "86.260(3)",
"specifier": "β",
"units": "Degrees^(1.0)",
"value": [
86.26
]
}
},
"lattice_param_c": {
"CellLengthC": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"error": 0.0006000000000000001,
"raw_units": "Å",
"raw_value": "12.7418(6)",
"specifier": "c",
"units": "Angstrom^(1.0)",
"value": [
12.7418
]
}
},
"lattice_param_gamma": {
"CellAngleGamma": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"error": 0.003,
"raw_units": "°",
"raw_value": "85.324(3)",
"specifier": "γ",
"units": "Degrees^(1.0)",
"value": [
85.324
]
}
},
"space_group": {
"SpaceGroup": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"specifier": "Space group",
"symbol": "P1̄"
}
},
"specifier": "Crystal system",
"system": "triclinic"
}
},
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
],
"smiles": []
},
"elements": [
"N",
"F",
"Pd",
"C",
"H",
"B"
]
},
"diffraction_params": {
"DiffractionParams": {
"absorption_coefficient": {
"AbsorptionCoefficient": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"raw_units": "mm−1",
"raw_value": "0.845",
"specifier": "μ(Mo-Kα)",
"units": "(10^3.0) * Meter^(-1.0)",
"value": [
0.845
]
}
},
"applied_temperature": {
"AppliedTemperature": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"raw_units": "K",
"raw_value": "183.2",
"specifier": "T",
"units": "Kelvin^(1.0)",
"value": [
183.2
]
}
},
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"specifier": "Space group",
"structure_factor": {
"F": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"raw_value": "624.00",
"specifier": "F(000)",
"value": [
624.0
]
}
},
"z": {
"Z": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"raw_value": "2",
"specifier": "Z",
"value": [
2.0
]
}
}
}
},
"formula_weight_no_dim": {
"FormulaWeightNoDim": {
"compound": {
"Compound": {
"names": [
"C20H22B2F8N6Pd"
]
}
},
"raw_value": "626.44",
"specifier": "Formula weight",
"value": [
626.44
]
}
},
"specifier": "Space group"
}
}
],
"tables": [
{
"caption": "Table 1 Data on the fluxionality",
"heading": 0,
"tde_raw_table": [
[
"Entry",
"Complex",
"T(coal.)/K",
"ΔG†/kJ mol−1",
"Solvent"
],
[
"1",
"[{CCC}PdBr]",
"350",
"70.9",
"d6-dmso"
],
[
"2",
"[{CNC}PdCl]Cl",
"308",
"59.3",
"CDCl3"
],
[
"3",
"[{CNC}PdCl]OTs",
"343",
"66.0",
"d6-dmso"
],
[
"4",
"[{CNC}PdBr]Br",
"278",
"52.9",
"CDCl3"
],
[
"5",
"[{CNC}PdBr]OTs",
"373",
"77.6",
"d6-dmso"
],
[
"6",
"[{CNC}PdI]I",
"208",
"41.9",
"CD2Cl2"
],
[
"7",
"[{CNC}PdI]OTs",
"338",
"70.9",
"d6-dmso"
],
[
"8",
"[{CNC}Pd(OH2)][BF4]2",
"\u003e353",
"\u003e73",
"CDCl3"
],
[
"9",
"[{CNC}PdCl]Cl",
"303",
"60.0",
"CD2Cl2"
],
[
"10",
"[{CNC}Pd(py)][BF4]2",
"\u003e403",
"\u003e73",
"d6-dmso"
],
[
"11",
"[{CNC′}PdBr]Br",
"303",
"57.4",
"CDCl3"
],
[
"12",
"[{CNC}Pd(OH2)][BF4]2",
"343",
"68.5",
"d6-dmso"
]
],
"tde_table": [
[
"[{CCC}PdBr]",
[
"1"
],
[
"Complex"
]
],
[
"350",
[
"1"
],
[
"T(coal.)/K"
]
],
[
"70.9",
[
"1"
],
[
"ΔG†/kJ mol−1"
]
],
[
"d6-dmso",
[
"1"
],
[
"Solvent"
]
],
[
"[{CNC}PdCl]Cl",
[
"2"
],
[
"Complex"
]
],
[
"308",
[
"2"
],
[
"T(coal.)/K"
]
],
[
"59.3",
[
"2"
],
[
"ΔG†/kJ mol−1"
]
],
[
"CDCl3",
[
"2"
],
[
"Solvent"
]
],
[
"[{CNC}PdCl]OTs",
[
"3"
],
[
"Complex"
]
],
[
"343",
[
"3"
],
[
"T(coal.)/K"
]
],
[
"66.0",
[
"3"
],
[
"ΔG†/kJ mol−1"
]
],
[
"d6-dmso",
[
"3"
],
[
"Solvent"
]
],
[
"[{CNC}PdBr]Br",
[
"4"
],
[
"Complex"
]
],
[
"278",
[
"4"
],
[
"T(coal.)/K"
]
],
[
"52.9",
[
"4"
],
[
"ΔG†/kJ mol−1"
]
],
[
"CDCl3",
[
"4"
],
[
"Solvent"
]
],
[
"[{CNC}PdBr]OTs",
[
"5"
],
[
"Complex"
]
],
[
"373",
[
"5"
],
[
"T(coal.)/K"
]
],
[
"77.6",
[
"5"
],
[
"ΔG†/kJ mol−1"
]
],
[
"d6-dmso",
[
"5"
],
[
"Solvent"
]
],
[
"[{CNC}PdI]I",
[
"6"
],
[
"Complex"
]
],
[
"208",
[
"6"
],
[
"T(coal.)/K"
]
],
[
"41.9",
[
"6"
],
[
"ΔG†/kJ mol−1"
]
],
[
"CD2Cl2",
[
"6"
],
[
"Solvent"
]
],
[
"[{CNC}PdI]OTs",
[
"7"
],
[
"Complex"
]
],
[
"338",
[
"7"
],
[
"T(coal.)/K"
]
],
[
"70.9",
[
"7"
],
[
"ΔG†/kJ mol−1"
]
],
[
"d6-dmso",
[
"7"
],
[
"Solvent"
]
],
[
"[{CNC}Pd(OH2)][BF4]2",
[
"8"
],
[
"Complex"
]
],
[
"\u003e353",
[
"8"
],
[
"T(coal.)/K"
]
],
[
"\u003e73",
[
"8"
],
[
"ΔG†/kJ mol−1"
]
],
[
"CDCl3",
[
"8"
],
[
"Solvent"
]
],
[
"[{CNC}PdCl]Cl",
[
"9"
],
[
"Complex"
]
],
[
"303",
[
"9"
],
[
"T(coal.)/K"
]
],
[
"60.0",
[
"9"
],
[
"ΔG†/kJ mol−1"
]
],
[
"CD2Cl2",
[
"9"
],
[
"Solvent"
]
],
[
"[{CNC}Pd(py)][BF4]2",
[
"10"
],
[
"Complex"
]
],
[
"\u003e403",
[
"10"
],
[
"T(coal.)/K"
]
],
[
"\u003e73",
[
"10"
],
[
"ΔG†/kJ mol−1"
]
],
[
"d6-dmso",
[
"10"
],
[
"Solvent"
]
],
[
"[{CNC′}PdBr]Br",
[
"11"
],
[
"Complex"
]
],
[
"303",
[
"11"
],
[
"T(coal.)/K"
]
],
[
"57.4",
[
"11"
],
[
"ΔG†/kJ mol−1"
]
],
[
"CDCl3",
[
"11"
],
[
"Solvent"
]
],
[
"[{CNC}Pd(OH2)][BF4]2",
[
"12"
],
[
"Complex"
]
],
[
"343",
[
"12"
],
[
"T(coal.)/K"
]
],
[
"68.5",
[
"12"
],
[
"ΔG†/kJ mol−1"
]
],
[
"d6-dmso",
[
"12"
],
[
"Solvent"
]
]
]
},
{
"caption": "Table 2 Selected bond lengths and angles for complex [{CNC}Pd(C5H4N)][BF4]2",
"heading": 0,
"tde_raw_table": [
[
"Bond lengths/Å",
"Bond lengths/Å"
],
[
"Pd(1)–N(5)",
"2.060(4)"
],
[
"Pd(1)–N(6)",
"2.017(4)"
],
[
"Pd(1)–C(11)",
"2.021(4)"
],
[
"Pd(1)–C(21)",
"2.027(4)"
],
[
"Bond angles/deg.",
"Bond angles/deg."
],
[
"N(5)–Pd(1)–C(11)",
"87.8(2)"
],
[
"N(5)–Pd(1)–C(21)",
"88.4(2)"
],
[
"N(6)–Pd(1)–C(11)",
"92.1(2)"
],
[
"N(6)–Pd(1)–C(21)",
"91.8(2)"
],
[
"N(5)–Pd(1)–N(6)",
"178.5(2)"
],
[
"C(11)–Pd(1)–C(21)",
"175.6(2)"
],
[
"Dihedral angles/deg.",
"Dihedral angles/deg."
],
[
"C(11)–Pd(1)–N(5)–C(1)",
"−41.1(3)"
],
[
"C(11)–Pd(1)–N(6)–C(1)",
"−65.1(3)"
],
[
"N(6)–Pd(1)–C(11)–N(2)",
"40.4(4)"
],
[
"N(6)–Pd(1)–C(21)–N(4)",
"39.2(5)"
]
],
"tde_table": [
[
"2.060(4)",
[
"Pd(1)–N(5)"
],
[
"Bond lengths/Å"
]
],
[
"2.017(4)",
[
"Pd(1)–N(6)"
],
[
"Bond lengths/Å"
]
],
[
"2.021(4)",
[
"Pd(1)–C(11)"
],
[
"Bond lengths/Å"
]
],
[
"2.027(4)",
[
"Pd(1)–C(21)"
],
[
"Bond lengths/Å"
]
],
[
"Bond angles/deg.",
[
"Bond angles/deg."
],
[
"Bond lengths/Å"
]
],
[
"87.8(2)",
[
"N(5)–Pd(1)–C(11)"
],
[
"Bond lengths/Å"
]
],
[
"88.4(2)",
[
"N(5)–Pd(1)–C(21)"
],
[
"Bond lengths/Å"
]
],
[
"92.1(2)",
[
"N(6)–Pd(1)–C(11)"
],
[
"Bond lengths/Å"
]
],
[
"91.8(2)",
[
"N(6)–Pd(1)–C(21)"
],
[
"Bond lengths/Å"
]
],
[
"178.5(2)",
[
"N(5)–Pd(1)–N(6)"
],
[
"Bond lengths/Å"
]
],
[
"175.6(2)",
[
"C(11)–Pd(1)–C(21)"
],
[
"Bond lengths/Å"
]
],
[
"Dihedral angles/deg.",
[
"Dihedral angles/deg."
],
[
"Bond lengths/Å"
]
],
[
"−41.1(3)",
[
"C(11)–Pd(1)–N(5)–C(1)"
],
[
"Bond lengths/Å"
]
],
[
"−65.1(3)",
[
"C(11)–Pd(1)–N(6)–C(1)"
],
[
"Bond lengths/Å"
]
],
[
"40.4(4)",
[
"N(6)–Pd(1)–C(11)–N(2)"
],
[
"Bond lengths/Å"
]
],
[
"39.2(5)",
[
"N(6)–Pd(1)–C(21)–N(4)"
],
[
"Bond lengths/Å"
]
]
]
},
{
"caption": "Table 3 Crystal data and structure refinement for [{CNC}Pd(C5H4N)][BF4]2",
"heading": 0,
"tde_raw_table": [
[
"Formula",
"C20H22B2F8N6Pd"
],
[
"Formula weight",
"626.44"
],
[
"Crystal dimensions/mm",
"0.07 × 0.07 × 0.12"
],
[
"Crystal system",
"triclinic"
],
[
"Space group",
"P1̄"
],
[
"a/Å",
"9.8872(5)"
],
[
"b/Å",
"9.9387(5)"
],
[
"c/Å",
"12.7418(6)"
],
[
"α/°",
"77.790(3)"
],
[
"β/°",
"86.260(3)"
],
[
"γ/°",
"85.324(3)"
],
[
"V/Å3",
"1218.2(1)"
],
[
"Z",
"2"
],
[
"F(000)",
"624.00"
],
[
"T/K",
"183.2"
],
[
"Dc/Mg m−3",
"1.708"
],
[
"μ(Mo-Kα)/mm−1",
"0.845"
],
[
"No. collected reflections",
"15462"
],
[
"No. unique reflections, Rint",
"5578, 0.047"
],
[
"No. of observed reflections",
"3701"
],
[
"No. of refined parameters",
"334"
],
[
"wR(F)",
"0.049"
],
[
"R[I \u003e 3σ(I)]",
"0.041"
],
[
"Goodness-of-fit",
"1.18"
],
[
"(Δρ) max, min/e Å−3",
"0.92, −0.50"
]
],
"tde_table": [
[
"626.44",
[
"Formula weight"
],
[
"C20H22B2F8N6Pd"
]
],
[
"0.07 × 0.07 × 0.12",
[
"Crystal dimensions/mm"
],
[
"C20H22B2F8N6Pd"
]
],
[
"triclinic",
[
"Crystal system"
],
[
"C20H22B2F8N6Pd"
]
],
[
"P1̄",
[
"Space group"
],
[
"C20H22B2F8N6Pd"
]
],
[
"9.8872(5)",
[
"a/Å"
],
[
"C20H22B2F8N6Pd"
]
],
[
"9.9387(5)",
[
"b/Å"
],
[
"C20H22B2F8N6Pd"
]
],
[
"12.7418(6)",
[
"c/Å"
],
[
"C20H22B2F8N6Pd"
]
],
[
"77.790(3)",
[
"α/°"
],
[
"C20H22B2F8N6Pd"
]
],
[
"86.260(3)",
[
"β/°"
],
[
"C20H22B2F8N6Pd"
]
],
[
"85.324(3)",
[
"γ/°"
],
[
"C20H22B2F8N6Pd"
]
],
[
"1218.2(1)",
[
"V/Å3"
],
[
"C20H22B2F8N6Pd"
]
],
[
"2",
[
"Z"
],
[
"C20H22B2F8N6Pd"
]
],
[
"624.00",
[
"F(000)"
],
[
"C20H22B2F8N6Pd"
]
],
[
"183.2",
[
"T/K"
],
[
"C20H22B2F8N6Pd"
]
],
[
"1.708",
[
"Dc/Mg m−3"
],
[
"C20H22B2F8N6Pd"
]
],
[
"0.845",
[
"μ(Mo-Kα)/mm−1"
],
[
"C20H22B2F8N6Pd"
]
],
[
"15462",
[
"No. collected reflections"
],
[
"C20H22B2F8N6Pd"
]
],
[
"5578, 0.047",
[
"No. unique reflections, Rint"
],
[
"C20H22B2F8N6Pd"
]
],
[
"3701",
[
"No. of observed reflections"
],
[
"C20H22B2F8N6Pd"
]
],
[
"334",
[
"No. of refined parameters"
],
[
"C20H22B2F8N6Pd"
]
],
[
"0.049",
[
"wR(F)"
],
[
"C20H22B2F8N6Pd"
]
],
[
"0.041",
[
"R[I \u003e 3σ(I)]"
],
[
"C20H22B2F8N6Pd"
]
],
[
"1.18",
[
"Goodness-of-fit"
],
[
"C20H22B2F8N6Pd"
]
],
[
"0.92, −0.50",
[
"(Δρ) max, min/e Å−3"
],
[
"C20H22B2F8N6Pd"
]
]
]
},
{
"caption": "Table 4 Comparison of experimental bond distances and angles for Pd{CEC}Br, 1\n(E = C), and [Pd{CEC}Br][Br], 2\n(E = N), with that of the calculated complexes Pd{CEC}Br, GS(1Br)\n(E = C), and Pd{CEC}Br+,GS(2Br)\n(E = N)",
"heading": 0,
"tde_raw_table": [
[
"",
"1",
"GS(1Br)",
"2",
"GS(2Br)"
],
[
"Bond lengths/Å",
"Bond lengths/Å",
"Bond lengths/Å",
"Bond lengths/Å",
"Bond lengths/Å"
],
[
"Pd–E",
"2.014",
"2.017",
"2.066",
"2.093"
],
[
"Pd–C(11)",
"2.00",
"2.035",
"2.020",
"2.034"
],
[
"Pd–Br",
"2.5388",
"2.558",
"2.4250",
"2.422"
],
[
"C(12)–C(13)",
"1.33",
"1.366",
"1.328",
"1.358"
],
[
"Bond angles/deg.",
"Bond angles/deg.",
"Bond angles/deg.",
"Bond angles/deg.",
"Bond angles/deg."
],
[
"C(11)–Pd–C(21)",
"170.9",
"172.2",
"173.2",
"174.9"
],
[
"E–Pd–C(11)",
"85.1",
"86.1",
"86.7",
"87.5"
],
[
"E–Pd–Br",
"179.6",
"180.0",
"178.9",
"180.0"
],
[
"Dihedral angles/deg.",
"Dihedral angles/deg.",
"Dihedral angles/deg.",
"Dihedral angles/deg.",
"Dihedral angles/deg."
],
[
"C(1)–E–Pd–C(11)",
"42.9",
"41.3",
"40.6",
"41.0"
],
[
"N(1)–C(7)–C(1)–C(6)",
"49.3",
"52.7",
"57.2",
"56.3"
],
[
"N(2)–C(11)–C(21)–N(4)",
"95.4",
"96.8",
"101.3",
"91.8"
]
],
"tde_table": [
[
"Bond lengths/Å",
[
"Bond lengths/Å"
],
[
"1"
]
],
[
"Bond lengths/Å",
[
"Bond lengths/Å"
],
[
"GS(1Br)"
]
],
[
"Bond lengths/Å",
[
"Bond lengths/Å"
],
[
"2"
]
],
[
"Bond lengths/Å",
[
"Bond lengths/Å"
],
[
"GS(2Br)"
]
],
[
"2.014",
[
"Pd–E"
],
[
"1"
]
],
[
"2.017",
[
"Pd–E"
],
[
"GS(1Br)"
]
],
[
"2.066",
[
"Pd–E"
],
[
"2"
]
],
[
"2.093",
[
"Pd–E"
],
[
"GS(2Br)"
]
],
[
"2.00",
[
"Pd–C(11)"
],
[
"1"
]
],
[
"2.035",
[
"Pd–C(11)"
],
[
"GS(1Br)"
]
],
[
"2.020",
[
"Pd–C(11)"
],
[
"2"
]
],
[
"2.034",
[
"Pd–C(11)"
],
[
"GS(2Br)"
]
],
[
"2.5388",
[
"Pd–Br"
],
[
"1"
]
],
[
"2.558",
[
"Pd–Br"
],
[
"GS(1Br)"
]
],
[
"2.4250",
[
"Pd–Br"
],
[
"2"
]
],
[
"2.422",
[
"Pd–Br"
],
[
"GS(2Br)"
]
],
[
"1.33",
[
"C(12)–C(13)"
],
[
"1"
]
],
[
"1.366",
[
"C(12)–C(13)"
],
[
"GS(1Br)"
]
],
[
"1.328",
[
"C(12)–C(13)"
],
[
"2"
]
],
[
"1.358",
[
"C(12)–C(13)"
],
[
"GS(2Br)"
]
],
[
"Bond angles/deg.",
[
"Bond angles/deg."
],
[
"1"
]
],
[
"Bond angles/deg.",
[
"Bond angles/deg."
],
[
"GS(1Br)"
]
],
[
"Bond angles/deg.",
[
"Bond angles/deg."
],
[
"2"
]
],
[
"Bond angles/deg.",
[
"Bond angles/deg."
],
[
"GS(2Br)"
]
],
[
"170.9",
[
"C(11)–Pd–C(21)"
],
[
"1"
]
],
[
"172.2",
[
"C(11)–Pd–C(21)"
],
[
"GS(1Br)"
]
],
[
"173.2",
[
"C(11)–Pd–C(21)"
],
[
"2"
]
],
[
"174.9",
[
"C(11)–Pd–C(21)"
],
[
"GS(2Br)"
]
],
[
"85.1",
[
"E–Pd–C(11)"
],
[
"1"
]
],
[
"86.1",
[
"E–Pd–C(11)"
],
[
"GS(1Br)"
]
],
[
"86.7",
[
"E–Pd–C(11)"
],
[
"2"
]
],
[
"87.5",
[
"E–Pd–C(11)"
],
[
"GS(2Br)"
]
],
[
"179.6",
[
"E–Pd–Br"
],
[
"1"
]
],
[
"180.0",
[
"E–Pd–Br"
],
[
"GS(1Br)"
]
],
[
"178.9",
[
"E–Pd–Br"
],
[
"2"
]
],
[
"180.0",
[
"E–Pd–Br"
],
[
"GS(2Br)"
]
],
[
"Dihedral angles/deg.",
[
"Dihedral angles/deg."
],
[
"1"
]
],
[
"Dihedral angles/deg.",
[
"Dihedral angles/deg."
],
[
"GS(1Br)"
]
],
[
"Dihedral angles/deg.",
[
"Dihedral angles/deg."
],
[
"2"
]
],
[
"Dihedral angles/deg.",
[
"Dihedral angles/deg."
],
[
"GS(2Br)"
]
],
[
"42.9",
[
"C(1)–E–Pd–C(11)"
],
[
"1"
]
],
[
"41.3",
[
"C(1)–E–Pd–C(11)"
],
[
"GS(1Br)"
]
],
[
"40.6",
[
"C(1)–E–Pd–C(11)"
],
[
"2"
]
],
[
"41.0",
[
"C(1)–E–Pd–C(11)"
],
[
"GS(2Br)"
]
],
[
"49.3",
[
"N(1)–C(7)–C(1)–C(6)"
],
[
"1"
]
],
[
"52.7",
[
"N(1)–C(7)–C(1)–C(6)"
],
[
"GS(1Br)"
]
],
[
"57.2",
[
"N(1)–C(7)–C(1)–C(6)"
],
[
"2"
]
],
[
"56.3",
[
"N(1)–C(7)–C(1)–C(6)"
],
[
"GS(2Br)"
]
],
[
"95.4",
[
"N(2)–C(11)–C(21)–N(4)"
],
[
"1"
]
],
[
"96.8",
[
"N(2)–C(11)–C(21)–N(4)"
],
[
"GS(1Br)"
]
],
[
"101.3",
[
"N(2)–C(11)–C(21)–N(4)"
],
[
"2"
]
],
[
"91.8",
[
"N(2)–C(11)–C(21)–N(4)"
],
[
"GS(2Br)"
]
]
]
},
{
"caption": "Table 5 Selected bond distance (Å), angles and dihedral angles (degrees) for the calculated complexes involved in the two-step fluxional process for [{CCC}PdX] and [{CNC}PdX]+\n(X = Cl, Br, I)",
"heading": 0,
"tde_raw_table": [
[
"",
"X = Cl",
"X = Cl",
"X = Cl",
"X = Br",
"X = Br",
"X = Br",
"X = I",
"X = I",
"X = I"
],
[
"",
"GS(1Cl)",
"TS(1Cl)",
"Int(1Cl)",
"GS(1Br)",
"TS(1Br)",
"Int(1Br)",
"GS(1I)",
"TS(1I)",
"Int(1I)"
],
[
"Pd–X",
"2.428",
"2.449",
"2.445",
"2.558",
"2.595",
"2.581",
"2.742",
"2.783",
"2.774"
],
[
"Pd–C(6)",
"2.015",
"2.048",
"2.055",
"2.018",
"2.049",
"2.060",
"2.020",
"2.056",
"2.065"
],
[
"Pd–C(11)",
"2.034",
"2.016",
"2.042",
"2.035",
"2.012",
"2.037",
"2.034",
"2.015",
"2.034"
],
[
"Pd–C(21)",
"2.034",
"2.067",
"2.042",
"2.035",
"2.067",
"2.040",
"2.034",
"2.055",
"2.034"
],
[
"C(6)–Pd–X",
"180.0",
"158.9",
"159.4",
"180.0",
"154.9",
"156.2",
"180.0",
"151.6",
"151.6"
],
[
"C(11)–Pd–C(21)",
"173.2",
"159.6",
"157.3",
"172.2",
"159.6",
"156.5",
"171.5",
"158.7",
"156.0"
],
[
"C(6)–C(1)–C(7)–N(1)",
"−52.2",
"−54.8",
"−49.6",
"−52.7",
"−54.9",
"−50.5",
"−52.9",
"−55.1",
"−49.2"
],
[
"C(6)–C(5)–C(8)–N(3)",
"−52.2",
"33.2",
"49.7",
"−52.7",
"27.6",
"49.1",
"−52.9",
"27.2",
"49.2"
]
],
"tde_table": [
[
"2.428",
[
"Pd–X"
],
[
"X = Cl",
"GS(1Cl)"
]
],
[
"2.449",
[
"Pd–X"
],
[
"X = Cl",
"TS(1Cl)"
]
],
[
"2.445",
[
"Pd–X"
],
[
"X = Cl",
"Int(1Cl)"
]
],
[
"2.558",
[
"Pd–X"
],
[
"X = Br",
"GS(1Br)"
]
],
[
"2.595",
[
"Pd–X"
],
[
"X = Br",
"TS(1Br)"
]
],
[
"2.581",
[
"Pd–X"
],
[
"X = Br",
"Int(1Br)"
]
],
[
"2.742",
[
"Pd–X"
],
[
"X = I",
"GS(1I)"
]
],
[
"2.783",
[
"Pd–X"
],
[
"X = I",
"TS(1I)"
]
],
[
"2.774",
[
"Pd–X"
],
[
"X = I",
"Int(1I)"
]
],
[
"2.015",
[
"Pd–C(6)"
],
[
"X = Cl",
"GS(1Cl)"
]
],
[
"2.048",
[
"Pd–C(6)"
],
[
"X = Cl",
"TS(1Cl)"
]
],
[
"2.055",
[
"Pd–C(6)"
],
[
"X = Cl",
"Int(1Cl)"
]
],
[
"2.018",
[
"Pd–C(6)"
],
[
"X = Br",
"GS(1Br)"
]
],
[
"2.049",
[
"Pd–C(6)"
],
[
"X = Br",
"TS(1Br)"
]
],
[
"2.060",
[
"Pd–C(6)"
],
[
"X = Br",
"Int(1Br)"
]
],
[
"2.020",
[
"Pd–C(6)"
],
[
"X = I",
"GS(1I)"
]
],
[
"2.056",
[
"Pd–C(6)"
],
[
"X = I",
"TS(1I)"
]
],
[
"2.065",
[
"Pd–C(6)"
],
[
"X = I",
"Int(1I)"
]
],
[
"2.034",
[
"Pd–C(11)"
],
[
"X = Cl",
"GS(1Cl)"
]
],
[
"2.016",
[
"Pd–C(11)"
],
[
"X = Cl",
"TS(1Cl)"
]
],
[
"2.042",
[
"Pd–C(11)"
],
[
"X = Cl",
"Int(1Cl)"
]
],
[
"2.035",
[
"Pd–C(11)"
],
[
"X = Br",
"GS(1Br)"
]
],
[
"2.012",
[
"Pd–C(11)"
],
[
"X = Br",
"TS(1Br)"
]
],
[
"2.037",
[
"Pd–C(11)"
],
[
"X = Br",
"Int(1Br)"
]
],
[
"2.034",
[
"Pd–C(11)"
],
[
"X = I",
"GS(1I)"
]
],
[
"2.015",
[
"Pd–C(11)"
],
[
"X = I",
"TS(1I)"
]
],
[
"2.034",
[
"Pd–C(11)"
],
[
"X = I",
"Int(1I)"
]
],
[
"2.034",
[
"Pd–C(21)"
],
[
"X = Cl",
"GS(1Cl)"
]
],
[
"2.067",
[
"Pd–C(21)"
],
[
"X = Cl",
"TS(1Cl)"
]
],
[
"2.042",
[
"Pd–C(21)"
],
[
"X = Cl",
"Int(1Cl)"
]
],
[
"2.035",
[
"Pd–C(21)"
],
[
"X = Br",
"GS(1Br)"
]
],
[
"2.067",
[
"Pd–C(21)"
],
[
"X = Br",
"TS(1Br)"
]
],
[
"2.040",
[
"Pd–C(21)"
],
[
"X = Br",
"Int(1Br)"
]
],
[
"2.034",
[
"Pd–C(21)"
],
[
"X = I",
"GS(1I)"
]
],
[
"2.055",
[
"Pd–C(21)"
],
[
"X = I",
"TS(1I)"
]
],
[
"2.034",
[
"Pd–C(21)"
],
[
"X = I",
"Int(1I)"
]
],
[
"180.0",
[
"C(6)–Pd–X"
],
[
"X = Cl",
"GS(1Cl)"
]
],
[
"158.9",
[
"C(6)–Pd–X"
],
[
"X = Cl",
"TS(1Cl)"
]
],
[
"159.4",
[
"C(6)–Pd–X"
],
[
"X = Cl",
"Int(1Cl)"
]
],
[
"180.0",
[
"C(6)–Pd–X"
],
[
"X = Br",
"GS(1Br)"
]
],
[
"154.9",
[
"C(6)–Pd–X"
],
[
"X = Br",
"TS(1Br)"
]
],
[
"156.2",
[
"C(6)–Pd–X"
],
[
"X = Br",
"Int(1Br)"
]
],
[
"180.0",
[
"C(6)–Pd–X"
],
[
"X = I",
"GS(1I)"
]
],
[
"151.6",
[
"C(6)–Pd–X"
],
[
"X = I",
"TS(1I)"
]
],
[
"151.6",
[
"C(6)–Pd–X"
],
[
"X = I",
"Int(1I)"
]
],
[
"173.2",
[
"C(11)–Pd–C(21)"
],
[
"X = Cl",
"GS(1Cl)"
]
],
[
"159.6",
[
"C(11)–Pd–C(21)"
],
[
"X = Cl",
"TS(1Cl)"
]
],
[
"157.3",
[
"C(11)–Pd–C(21)"
],
[
"X = Cl",
"Int(1Cl)"
]
],
[
"172.2",
[
"C(11)–Pd–C(21)"
],
[
"X = Br",
"GS(1Br)"
]
],
[
"159.6",
[
"C(11)–Pd–C(21)"
],
[
"X = Br",
"TS(1Br)"
]
],
[
"156.5",
[
"C(11)–Pd–C(21)"
],
[
"X = Br",
"Int(1Br)"
]
],
[
"171.5",
[
"C(11)–Pd–C(21)"
],
[
"X = I",
"GS(1I)"
]
],
[
"158.7",
[
"C(11)–Pd–C(21)"
],
[
"X = I",
"TS(1I)"
]
],
[
"156.0",
[
"C(11)–Pd–C(21)"
],
[
"X = I",
"Int(1I)"
]
],
[
"−52.2",
[
"C(6)–C(1)–C(7)–N(1)"
],
[
"X = Cl",
"GS(1Cl)"
]
],
[
"−54.8",
[
"C(6)–C(1)–C(7)–N(1)"
],
[
"X = Cl",
"TS(1Cl)"
]
],
[
"−49.6",
[
"C(6)–C(1)–C(7)–N(1)"
],
[
"X = Cl",
"Int(1Cl)"
]
],
[
"−52.7",
[
"C(6)–C(1)–C(7)–N(1)"
],
[
"X = Br",
"GS(1Br)"
]
],
[
"−54.9",
[
"C(6)–C(1)–C(7)–N(1)"
],
[
"X = Br",
"TS(1Br)"
]
],
[
"−50.5",
[
"C(6)–C(1)–C(7)–N(1)"
],
[
"X = Br",
"Int(1Br)"
]
],
[
"−52.9",
[
"C(6)–C(1)–C(7)–N(1)"
],
[
"X = I",
"GS(1I)"
]
],
[
"−55.1",
[
"C(6)–C(1)–C(7)–N(1)"
],
[
"X = I",
"TS(1I)"
]
],
[
"−49.2",
[
"C(6)–C(1)–C(7)–N(1)"
],
[
"X = I",
"Int(1I)"
]
],
[
"−52.2",
[
"C(6)–C(5)–C(8)–N(3)"
],
[
"X = Cl",
"GS(1Cl)"
]
],
[
"33.2",
[
"C(6)–C(5)–C(8)–N(3)"
],
[
"X = Cl",
"TS(1Cl)"
]
],
[
"49.7",
[
"C(6)–C(5)–C(8)–N(3)"
],
[
"X = Cl",
"Int(1Cl)"
]
],
[
"−52.7",
[
"C(6)–C(5)–C(8)–N(3)"
],
[
"X = Br",
"GS(1Br)"
]
],
[
"27.6",
[
"C(6)–C(5)–C(8)–N(3)"
],
[
"X = Br",
"TS(1Br)"
]
],
[
"49.1",
[
"C(6)–C(5)–C(8)–N(3)"
],
[
"X = Br",
"Int(1Br)"
]
],
[
"−52.9",
[
"C(6)–C(5)–C(8)–N(3)"
],
[
"X = I",
"GS(1I)"
]
],
[
"27.2",
[
"C(6)–C(5)–C(8)–N(3)"
],
[
"X = I",
"TS(1I)"
]
],
[
"49.2",
[
"C(6)–C(5)–C(8)–N(3)"
],
[
"X = I",
"Int(1I)"
]
]
]
},
{
"caption": "",
"heading": 0,
"tde_raw_table": [
[
"",
"GS(2Cl)",
"TS(2Cl)",
"Int(2Cl)",
"GS(2Br)",
"TS(2Br)",
"Int(2Br)",
"GS(2I)",
"TS(2I)",
"Int(2I)"
],
[
"Pd–X",
"2.294",
"2.300",
"2.308",
"2.422",
"2.436",
"2.437",
"2.607",
"2.630",
"2.626"
],
[
"Pd–N(5)",
"2.081",
"2.159",
"2.174",
"2.093",
"2.167",
"2.193",
"2.104",
"2.182",
"2.226"
],
[
"Pd–C(11)",
"2.031",
"2.029",
"2.046",
"2.034",
"2.021",
"2.046",
"2.037",
"2.013",
"2.035"
],
[
"Pd–C(21)",
"2.031",
"2.064",
"2.046",
"2.034",
"2.068",
"2.037",
"2.037",
"2.067",
"2.035"
],
[
"N(5)–Pd-X",
"180.0",
"162.3",
"158.6",
"180.0",
"158.8",
"155.1",
"180.0",
"153.5",
"147.9"
],
[
"C(11)–Pd–C(21)",
"175.8",
"163.6",
"161.0",
"174.9",
"163.8",
"161.1",
"173.8",
"164.1",
"160.8"
],
[
"N(5)–C(1)–C(7)–N(1)",
"−55.9",
"−66.5",
"−61.3",
"−56.4",
"−67.2",
"−61.2",
"−56.9",
"−66.4",
"−60.9"
],
[
"N(5)–C(5)–C(8)–N(3)",
"−55.9",
"50.9",
"61.3",
"−56.4",
"43.6",
"61.7",
"−56.9",
"33.2",
"60.9"
]
],
"tde_table": [
[
"2.294",
[
"Pd–X"
],
[
"GS(2Cl)"
]
],
[
"2.300",
[
"Pd–X"
],
[
"TS(2Cl)"
]
],
[
"2.308",
[
"Pd–X"
],
[
"Int(2Cl)"
]
],
[
"2.422",
[
"Pd–X"
],
[
"GS(2Br)"
]
],
[
"2.436",
[
"Pd–X"
],
[
"TS(2Br)"
]
],
[
"2.437",
[
"Pd–X"
],
[
"Int(2Br)"
]
],
[
"2.607",
[
"Pd–X"
],
[
"GS(2I)"
]
],
[
"2.630",
[
"Pd–X"
],
[
"TS(2I)"
]
],
[
"2.626",
[
"Pd–X"
],
[
"Int(2I)"
]
],
[
"2.081",
[
"Pd–N(5)"
],
[
"GS(2Cl)"
]
],
[
"2.159",
[
"Pd–N(5)"
],
[
"TS(2Cl)"
]
],
[
"2.174",
[
"Pd–N(5)"
],
[
"Int(2Cl)"
]
],
[
"2.093",
[
"Pd–N(5)"
],
[
"GS(2Br)"
]
],
[
"2.167",
[
"Pd–N(5)"
],
[
"TS(2Br)"
]
],
[
"2.193",
[
"Pd–N(5)"
],
[
"Int(2Br)"
]
],
[
"2.104",
[
"Pd–N(5)"
],
[
"GS(2I)"
]
],
[
"2.182",
[
"Pd–N(5)"
],
[
"TS(2I)"
]
],
[
"2.226",
[
"Pd–N(5)"
],
[
"Int(2I)"
]
],
[
"2.031",
[
"Pd–C(11)"
],
[
"GS(2Cl)"
]
],
[
"2.029",
[
"Pd–C(11)"
],
[
"TS(2Cl)"
]
],
[
"2.046",
[
"Pd–C(11)"
],
[
"Int(2Cl)"
]
],
[
"2.034",
[
"Pd–C(11)"
],
[
"GS(2Br)"
]
],
[
"2.021",
[
"Pd–C(11)"
],
[
"TS(2Br)"
]
],
[
"2.046",
[
"Pd–C(11)"
],
[
"Int(2Br)"
]
],
[
"2.037",
[
"Pd–C(11)"
],
[
"GS(2I)"
]
],
[
"2.013",
[
"Pd–C(11)"
],
[
"TS(2I)"
]
],
[
"2.035",
[
"Pd–C(11)"
],
[
"Int(2I)"
]
],
[
"2.031",
[
"Pd–C(21)"
],
[
"GS(2Cl)"
]
],
[
"2.064",
[
"Pd–C(21)"
],
[
"TS(2Cl)"
]
],
[
"2.046",
[
"Pd–C(21)"
],
[
"Int(2Cl)"
]
],
[
"2.034",
[
"Pd–C(21)"
],
[
"GS(2Br)"
]
],
[
"2.068",
[
"Pd–C(21)"
],
[
"TS(2Br)"
]
],
[
"2.037",
[
"Pd–C(21)"
],
[
"Int(2Br)"
]
],
[
"2.037",
[
"Pd–C(21)"
],
[
"GS(2I)"
]
],
[
"2.067",
[
"Pd–C(21)"
],
[
"TS(2I)"
]
],
[
"2.035",
[
"Pd–C(21)"
],
[
"Int(2I)"
]
],
[
"180.0",
[
"N(5)–Pd-X"
],
[
"GS(2Cl)"
]
],
[
"162.3",
[
"N(5)–Pd-X"
],
[
"TS(2Cl)"
]
],
[
"158.6",
[
"N(5)–Pd-X"
],
[
"Int(2Cl)"
]
],
[
"180.0",
[
"N(5)–Pd-X"
],
[
"GS(2Br)"
]
],
[
"158.8",
[
"N(5)–Pd-X"
],
[
"TS(2Br)"
]
],
[
"155.1",
[
"N(5)–Pd-X"
],
[
"Int(2Br)"
]
],
[
"180.0",
[
"N(5)–Pd-X"
],
[
"GS(2I)"
]
],
[
"153.5",
[
"N(5)–Pd-X"
],
[
"TS(2I)"
]
],
[
"147.9",
[
"N(5)–Pd-X"
],
[
"Int(2I)"
]
],
[
"175.8",
[
"C(11)–Pd–C(21)"
],
[
"GS(2Cl)"
]
],
[
"163.6",
[
"C(11)–Pd–C(21)"
],
[
"TS(2Cl)"
]
],
[
"161.0",
[
"C(11)–Pd–C(21)"
],
[
"Int(2Cl)"
]
],
[
"174.9",
[
"C(11)–Pd–C(21)"
],
[
"GS(2Br)"
]
],
[
"163.8",
[
"C(11)–Pd–C(21)"
],
[
"TS(2Br)"
]
],
[
"161.1",
[
"C(11)–Pd–C(21)"
],
[
"Int(2Br)"
]
],
[
"173.8",
[
"C(11)–Pd–C(21)"
],
[
"GS(2I)"
]
],
[
"164.1",
[
"C(11)–Pd–C(21)"
],
[
"TS(2I)"
]
],
[
"160.8",
[
"C(11)–Pd–C(21)"
],
[
"Int(2I)"
]
],
[
"−55.9",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"GS(2Cl)"
]
],
[
"−66.5",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"TS(2Cl)"
]
],
[
"−61.3",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"Int(2Cl)"
]
],
[
"−56.4",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"GS(2Br)"
]
],
[
"−67.2",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"TS(2Br)"
]
],
[
"−61.2",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"Int(2Br)"
]
],
[
"−56.9",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"GS(2I)"
]
],
[
"−66.4",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"TS(2I)"
]
],
[
"−60.9",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"Int(2I)"
]
],
[
"−55.9",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"GS(2Cl)"
]
],
[
"50.9",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"TS(2Cl)"
]
],
[
"61.3",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"Int(2Cl)"
]
],
[
"−56.4",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"GS(2Br)"
]
],
[
"43.6",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"TS(2Br)"
]
],
[
"61.7",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"Int(2Br)"
]
],
[
"−56.9",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"GS(2I)"
]
],
[
"33.2",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"TS(2I)"
]
],
[
"60.9",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"Int(2I)"
]
]
]
},
{
"caption": "Table 6 Activation energy and relative energy (kJ mol−1) of the intermediate for the two-step fluxional process for [{CCC}PdX] and [{CNC}PdX]+\n(X = Cl, Br, I). See Scheme 1 for definition of ΔE† and ΔE. GP stands for Gas Phase calculations at the B3PW91 model and PCM corresponds to calculations with a continuum model for the solvent on the B3PW91 optimized geometries",
"heading": 0,
"tde_raw_table": [
[
"",
"[{CCC}PdX]",
"[{CCC}PdX]",
"[{CCC}PdX]",
"[{CCC}PdX]",
"[{CNC}PdX]+",
"[{CNC}PdX]+",
"[{CNC}PdX]+",
"[{CNC}PdX]+"
],
[
"",
"ΔE†",
"ΔE†",
"ΔE",
"ΔE",
"ΔE†",
"ΔE†",
"ΔE",
"ΔE"
],
[
"",
"GP",
"PCM",
"GP",
"PCM",
"GP",
"PCM",
"GP",
"PCM"
],
[
"X = Cl",
"69.9",
"69.5",
"68.0",
"68.9",
"73.2",
"75.5",
"74.9",
"71.8"
],
[
"X = Br",
"71.4",
"72.3",
"68.2",
"71.2",
"73.0",
"75.3",
"72.3",
"66.6"
],
[
"X = I",
"72.5",
"72.4",
"69.0",
"66.5",
"72.9",
"79.3",
"69.7",
"67.2"
]
],
"tde_table": [
[
"69.9",
[
"X = Cl"
],
[
"[{CCC}PdX]",
"ΔE†",
"GP"
]
],
[
"69.5",
[
"X = Cl"
],
[
"[{CCC}PdX]",
"ΔE†",
"PCM"
]
],
[
"68.0",
[
"X = Cl"
],
[
"[{CCC}PdX]",
"ΔE",
"GP"
]
],
[
"68.9",
[
"X = Cl"
],
[
"[{CCC}PdX]",
"ΔE",
"PCM"
]
],
[
"73.2",
[
"X = Cl"
],
[
"[{CNC}PdX]+",
"ΔE†",
"GP"
]
],
[
"75.5",
[
"X = Cl"
],
[
"[{CNC}PdX]+",
"ΔE†",
"PCM"
]
],
[
"74.9",
[
"X = Cl"
],
[
"[{CNC}PdX]+",
"ΔE",
"GP"
]
],
[
"71.8",
[
"X = Cl"
],
[
"[{CNC}PdX]+",
"ΔE",
"PCM"
]
],
[
"71.4",
[
"X = Br"
],
[
"[{CCC}PdX]",
"ΔE†",
"GP"
]
],
[
"72.3",
[
"X = Br"
],
[
"[{CCC}PdX]",
"ΔE†",
"PCM"
]
],
[
"68.2",
[
"X = Br"
],
[
"[{CCC}PdX]",
"ΔE",
"GP"
]
],
[
"71.2",
[
"X = Br"
],
[
"[{CCC}PdX]",
"ΔE",
"PCM"
]
],
[
"73.0",
[
"X = Br"
],
[
"[{CNC}PdX]+",
"ΔE†",
"GP"
]
],
[
"75.3",
[
"X = Br"
],
[
"[{CNC}PdX]+",
"ΔE†",
"PCM"
]
],
[
"72.3",
[
"X = Br"
],
[
"[{CNC}PdX]+",
"ΔE",
"GP"
]
],
[
"66.6",
[
"X = Br"
],
[
"[{CNC}PdX]+",
"ΔE",
"PCM"
]
],
[
"72.5",
[
"X = I"
],
[
"[{CCC}PdX]",
"ΔE†",
"GP"
]
],
[
"72.4",
[
"X = I"
],
[
"[{CCC}PdX]",
"ΔE†",
"PCM"
]
],
[
"69.0",
[
"X = I"
],
[
"[{CCC}PdX]",
"ΔE",
"GP"
]
],
[
"66.5",
[
"X = I"
],
[
"[{CCC}PdX]",
"ΔE",
"PCM"
]
],
[
"72.9",
[
"X = I"
],
[
"[{CNC}PdX]+",
"ΔE†",
"GP"
]
],
[
"79.3",
[
"X = I"
],
[
"[{CNC}PdX]+",
"ΔE†",
"PCM"
]
],
[
"69.7",
[
"X = I"
],
[
"[{CNC}PdX]+",
"ΔE",
"GP"
]
],
[
"67.2",
[
"X = I"
],
[
"[{CNC}PdX]+",
"ΔE",
"PCM"
]
]
]
},
{
"caption": "Table 7 Selected bond distance (Å), angles and dihedral angles (degrees) for the calculated complexes involved in the two-step fluxional process for [{CNC}PdX2]\n(X = Cl, Br, I)",
"heading": 0,
"tde_raw_table": [
[
"",
"X = Cl",
"X = Cl",
"X = Cl",
"X = Br",
"X = Br",
"X = Br",
"X = I",
"X = I",
"X = I"
],
[
"",
"GS(2Cl2)",
"TS(2Cl2)",
"Int(2Cl2)",
"GS(2Br2)",
"TS(2Br2)",
"Int(2Br2)",
"GS(2I2)",
"TS(2I2)",
"Int(2I2)"
],
[
"Pd–X",
"2.390",
"2.367",
"2.370",
"2.531",
"2.503",
"2.505",
"2.730",
"2.695",
"2.695"
],
[
"Pd–N(5)",
"2.578",
"2.657",
"2.753",
"2.554",
"2.635",
"2.735",
"2.525",
"2.605",
"2.713"
],
[
"Pd–C(11)",
"2.015",
"2.016",
"2.023",
"2.015",
"2.015",
"2.021",
"2.017",
"2.016",
"2.022"
],
[
"Pd–C(21)",
"2.023",
"2.021",
"2.022",
"2.020",
"2.020",
"2.021",
"2.018",
"2.018",
"2.022"
],
[
"N(5)–Pd–X",
"94.4",
"93.9",
"99.0",
"96.3",
"94.2",
"99.3",
"98.7",
"94.9",
"100.2"
],
[
"N(5)–Pd–C(11)",
"85.4",
"90.7",
"88.1",
"85.3",
"90.5",
"88.3",
"86.0",
"90.5",
"88.5"
],
[
"C(11)–Pd–C(21)",
"168.6",
"172.0",
"175.4",
"169.9",
"172.3",
"176.1",
"171.9",
"173.2",
"176.5"
],
[
"N(5)–C(1)–C(7)–N(1)",
"−63.1",
"−94.4",
"−93.1",
"−56.9",
"−91.3",
"−92.3",
"−53.2",
"−87.4",
"−90.7"
],
[
"N(5)–C(5)–C(8)–N(3)",
"−47.0",
"31.1",
"93.2",
"−51.6",
"24.8",
"92.3",
"−53.0",
"19.2",
"90.7"
]
],
"tde_table": [
[
"2.390",
[
"Pd–X"
],
[
"X = Cl",
"GS(2Cl2)"
]
],
[
"2.367",
[
"Pd–X"
],
[
"X = Cl",
"TS(2Cl2)"
]
],
[
"2.370",
[
"Pd–X"
],
[
"X = Cl",
"Int(2Cl2)"
]
],
[
"2.531",
[
"Pd–X"
],
[
"X = Br",
"GS(2Br2)"
]
],
[
"2.503",
[
"Pd–X"
],
[
"X = Br",
"TS(2Br2)"
]
],
[
"2.505",
[
"Pd–X"
],
[
"X = Br",
"Int(2Br2)"
]
],
[
"2.730",
[
"Pd–X"
],
[
"X = I",
"GS(2I2)"
]
],
[
"2.695",
[
"Pd–X"
],
[
"X = I",
"TS(2I2)"
]
],
[
"2.695",
[
"Pd–X"
],
[
"X = I",
"Int(2I2)"
]
],
[
"2.578",
[
"Pd–N(5)"
],
[
"X = Cl",
"GS(2Cl2)"
]
],
[
"2.657",
[
"Pd–N(5)"
],
[
"X = Cl",
"TS(2Cl2)"
]
],
[
"2.753",
[
"Pd–N(5)"
],
[
"X = Cl",
"Int(2Cl2)"
]
],
[
"2.554",
[
"Pd–N(5)"
],
[
"X = Br",
"GS(2Br2)"
]
],
[
"2.635",
[
"Pd–N(5)"
],
[
"X = Br",
"TS(2Br2)"
]
],
[
"2.735",
[
"Pd–N(5)"
],
[
"X = Br",
"Int(2Br2)"
]
],
[
"2.525",
[
"Pd–N(5)"
],
[
"X = I",
"GS(2I2)"
]
],
[
"2.605",
[
"Pd–N(5)"
],
[
"X = I",
"TS(2I2)"
]
],
[
"2.713",
[
"Pd–N(5)"
],
[
"X = I",
"Int(2I2)"
]
],
[
"2.015",
[
"Pd–C(11)"
],
[
"X = Cl",
"GS(2Cl2)"
]
],
[
"2.016",
[
"Pd–C(11)"
],
[
"X = Cl",
"TS(2Cl2)"
]
],
[
"2.023",
[
"Pd–C(11)"
],
[
"X = Cl",
"Int(2Cl2)"
]
],
[
"2.015",
[
"Pd–C(11)"
],
[
"X = Br",
"GS(2Br2)"
]
],
[
"2.015",
[
"Pd–C(11)"
],
[
"X = Br",
"TS(2Br2)"
]
],
[
"2.021",
[
"Pd–C(11)"
],
[
"X = Br",
"Int(2Br2)"
]
],
[
"2.017",
[
"Pd–C(11)"
],
[
"X = I",
"GS(2I2)"
]
],
[
"2.016",
[
"Pd–C(11)"
],
[
"X = I",
"TS(2I2)"
]
],
[
"2.022",
[
"Pd–C(11)"
],
[
"X = I",
"Int(2I2)"
]
],
[
"2.023",
[
"Pd–C(21)"
],
[
"X = Cl",
"GS(2Cl2)"
]
],
[
"2.021",
[
"Pd–C(21)"
],
[
"X = Cl",
"TS(2Cl2)"
]
],
[
"2.022",
[
"Pd–C(21)"
],
[
"X = Cl",
"Int(2Cl2)"
]
],
[
"2.020",
[
"Pd–C(21)"
],
[
"X = Br",
"GS(2Br2)"
]
],
[
"2.020",
[
"Pd–C(21)"
],
[
"X = Br",
"TS(2Br2)"
]
],
[
"2.021",
[
"Pd–C(21)"
],
[
"X = Br",
"Int(2Br2)"
]
],
[
"2.018",
[
"Pd–C(21)"
],
[
"X = I",
"GS(2I2)"
]
],
[
"2.018",
[
"Pd–C(21)"
],
[
"X = I",
"TS(2I2)"
]
],
[
"2.022",
[
"Pd–C(21)"
],
[
"X = I",
"Int(2I2)"
]
],
[
"94.4",
[
"N(5)–Pd–X"
],
[
"X = Cl",
"GS(2Cl2)"
]
],
[
"93.9",
[
"N(5)–Pd–X"
],
[
"X = Cl",
"TS(2Cl2)"
]
],
[
"99.0",
[
"N(5)–Pd–X"
],
[
"X = Cl",
"Int(2Cl2)"
]
],
[
"96.3",
[
"N(5)–Pd–X"
],
[
"X = Br",
"GS(2Br2)"
]
],
[
"94.2",
[
"N(5)–Pd–X"
],
[
"X = Br",
"TS(2Br2)"
]
],
[
"99.3",
[
"N(5)–Pd–X"
],
[
"X = Br",
"Int(2Br2)"
]
],
[
"98.7",
[
"N(5)–Pd–X"
],
[
"X = I",
"GS(2I2)"
]
],
[
"94.9",
[
"N(5)–Pd–X"
],
[
"X = I",
"TS(2I2)"
]
],
[
"100.2",
[
"N(5)–Pd–X"
],
[
"X = I",
"Int(2I2)"
]
],
[
"85.4",
[
"N(5)–Pd–C(11)"
],
[
"X = Cl",
"GS(2Cl2)"
]
],
[
"90.7",
[
"N(5)–Pd–C(11)"
],
[
"X = Cl",
"TS(2Cl2)"
]
],
[
"88.1",
[
"N(5)–Pd–C(11)"
],
[
"X = Cl",
"Int(2Cl2)"
]
],
[
"85.3",
[
"N(5)–Pd–C(11)"
],
[
"X = Br",
"GS(2Br2)"
]
],
[
"90.5",
[
"N(5)–Pd–C(11)"
],
[
"X = Br",
"TS(2Br2)"
]
],
[
"88.3",
[
"N(5)–Pd–C(11)"
],
[
"X = Br",
"Int(2Br2)"
]
],
[
"86.0",
[
"N(5)–Pd–C(11)"
],
[
"X = I",
"GS(2I2)"
]
],
[
"90.5",
[
"N(5)–Pd–C(11)"
],
[
"X = I",
"TS(2I2)"
]
],
[
"88.5",
[
"N(5)–Pd–C(11)"
],
[
"X = I",
"Int(2I2)"
]
],
[
"168.6",
[
"C(11)–Pd–C(21)"
],
[
"X = Cl",
"GS(2Cl2)"
]
],
[
"172.0",
[
"C(11)–Pd–C(21)"
],
[
"X = Cl",
"TS(2Cl2)"
]
],
[
"175.4",
[
"C(11)–Pd–C(21)"
],
[
"X = Cl",
"Int(2Cl2)"
]
],
[
"169.9",
[
"C(11)–Pd–C(21)"
],
[
"X = Br",
"GS(2Br2)"
]
],
[
"172.3",
[
"C(11)–Pd–C(21)"
],
[
"X = Br",
"TS(2Br2)"
]
],
[
"176.1",
[
"C(11)–Pd–C(21)"
],
[
"X = Br",
"Int(2Br2)"
]
],
[
"171.9",
[
"C(11)–Pd–C(21)"
],
[
"X = I",
"GS(2I2)"
]
],
[
"173.2",
[
"C(11)–Pd–C(21)"
],
[
"X = I",
"TS(2I2)"
]
],
[
"176.5",
[
"C(11)–Pd–C(21)"
],
[
"X = I",
"Int(2I2)"
]
],
[
"−63.1",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"X = Cl",
"GS(2Cl2)"
]
],
[
"−94.4",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"X = Cl",
"TS(2Cl2)"
]
],
[
"−93.1",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"X = Cl",
"Int(2Cl2)"
]
],
[
"−56.9",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"X = Br",
"GS(2Br2)"
]
],
[
"−91.3",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"X = Br",
"TS(2Br2)"
]
],
[
"−92.3",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"X = Br",
"Int(2Br2)"
]
],
[
"−53.2",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"X = I",
"GS(2I2)"
]
],
[
"−87.4",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"X = I",
"TS(2I2)"
]
],
[
"−90.7",
[
"N(5)–C(1)–C(7)–N(1)"
],
[
"X = I",
"Int(2I2)"
]
],
[
"−47.0",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"X = Cl",
"GS(2Cl2)"
]
],
[
"31.1",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"X = Cl",
"TS(2Cl2)"
]
],
[
"93.2",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"X = Cl",
"Int(2Cl2)"
]
],
[
"−51.6",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"X = Br",
"GS(2Br2)"
]
],
[
"24.8",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"X = Br",
"TS(2Br2)"
]
],
[
"92.3",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"X = Br",
"Int(2Br2)"
]
],
[
"−53.0",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"X = I",
"GS(2I2)"
]
],
[
"19.2",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"X = I",
"TS(2I2)"
]
],
[
"90.7",
[
"N(5)–C(5)–C(8)–N(3)"
],
[
"X = I",
"Int(2I2)"
]
]
]
},
{
"caption": "Table 8 Activation energy and relative energy (kJ mol−1) of the intermediate for the two-step fluxional process [{CNC}PdX2]\n(X = Cl, Br, I). See Scheme 1 for definition of ΔE† and ΔE. GP stands for Gas Phase calculations at the B3PW91 model and PCM corresponds to calculation with a continuum model for the solvent on the B3PW91 optimized geometries",
"heading": 0,
"tde_raw_table": [
[
"",
"ΔE†",
"ΔE†",
"ΔE",
"ΔE"
],
[
"",
"GP",
"PCM",
"GP",
"PCM"
],
[
"X = Cl",
"11.2",
"10.4",
"0.2",
"0.8"
],
[
"X = Br",
"10.3",
"11.9",
"−4.1",
"−1.4"
],
[
"X = I",
"10.1",
"12.8",
"−8.0",
"−3.0"
]
],
"tde_table": [
[
"11.2",
[
"X = Cl"
],
[
"ΔE†",
"GP"
]
],
[
"10.4",
[
"X = Cl"
],
[
"ΔE†",
"PCM"
]
],
[
"0.2",
[
"X = Cl"
],
[
"ΔE",
"GP"
]
],
[
"0.8",
[
"X = Cl"
],
[
"ΔE",
"PCM"
]
],
[
"10.3",
[
"X = Br"
],
[
"ΔE†",
"GP"
]
],
[
"11.9",
[
"X = Br"
],
[
"ΔE†",
"PCM"
]
],
[
"−4.1",
[
"X = Br"
],
[
"ΔE",
"GP"
]
],
[
"−1.4",
[
"X = Br"
],
[
"ΔE",
"PCM"
]
],
[
"10.1",
[
"X = I"
],
[
"ΔE†",
"GP"
]
],
[
"12.8",
[
"X = I"
],
[
"ΔE†",
"PCM"
]
],
[
"−8.0",
[
"X = I"
],
[
"ΔE",
"GP"
]
],
[
"−3.0",
[
"X = I"
],
[
"ΔE",
"PCM"
]
]
]
}
]
}
]