0063c283-59fd-4d72-a5eb-4f94750007262020-06-24T12:52:04.202395SUCCESS0063c283-59fd-4d72-a5eb-4f9475000726.htmlTable 1 Data on the fluxionality0[{CCC}PdBr]1Complex3501T(coal.)/K70.91ΔG†/kJ mol−1d6-dmso1Solvent[{CNC}PdCl]Cl2Complex3082T(coal.)/K59.32ΔG†/kJ mol−1CDCl32Solvent[{CNC}PdCl]OTs3Complex3433T(coal.)/K66.03ΔG†/kJ mol−1d6-dmso3Solvent[{CNC}PdBr]Br4Complex2784T(coal.)/K52.94ΔG†/kJ mol−1CDCl34Solvent[{CNC}PdBr]OTs5Complex3735T(coal.)/K77.65ΔG†/kJ mol−1d6-dmso5Solvent[{CNC}PdI]I6Complex2086T(coal.)/K41.96ΔG†/kJ mol−1CD2Cl26Solvent[{CNC}PdI]OTs7Complex3387T(coal.)/K70.97ΔG†/kJ mol−1d6-dmso7Solvent[{CNC}Pd(OH2)][BF4]28Complex>3538T(coal.)/K>738ΔG†/kJ mol−1CDCl38Solvent[{CNC}PdCl]Cl9Complex3039T(coal.)/K60.09ΔG†/kJ mol−1CD2Cl29Solvent[{CNC}Pd(py)][BF4]210Complex>40310T(coal.)/K>7310ΔG†/kJ mol−1d6-dmso10Solvent[{CNC′}PdBr]Br11Complex30311T(coal.)/K57.411ΔG†/kJ mol−1CDCl311Solvent[{CNC}Pd(OH2)][BF4]212Complex34312T(coal.)/K68.512ΔG†/kJ mol−1d6-dmso12SolventEntryComplexT(coal.)/KΔG†/kJ mol−1Solvent1[{CCC}PdBr]35070.9d6-dmso2[{CNC}PdCl]Cl30859.3CDCl33[{CNC}PdCl]OTs34366.0d6-dmso4[{CNC}PdBr]Br27852.9CDCl35[{CNC}PdBr]OTs37377.6d6-dmso6[{CNC}PdI]I20841.9CD2Cl27[{CNC}PdI]OTs33870.9d6-dmso8[{CNC}Pd(OH2)][BF4]2>353>73CDCl39[{CNC}PdCl]Cl30360.0CD2Cl210[{CNC}Pd(py)][BF4]2>403>73d6-dmso11[{CNC′}PdBr]Br30357.4CDCl312[{CNC}Pd(OH2)][BF4]234368.5d6-dmsoTable 2 Selected bond lengths and angles for complex [{CNC}Pd(C5H4N)][BF4]202.060(4)Pd(1)–N(5)Bond lengths/Å2.017(4)Pd(1)–N(6)Bond lengths/Å2.021(4)Pd(1)–C(11)Bond lengths/Å2.027(4)Pd(1)–C(21)Bond lengths/ÅBond angles/deg.Bond angles/deg.Bond lengths/Å87.8(2)N(5)–Pd(1)–C(11)Bond lengths/Å88.4(2)N(5)–Pd(1)–C(21)Bond lengths/Å92.1(2)N(6)–Pd(1)–C(11)Bond lengths/Å91.8(2)N(6)–Pd(1)–C(21)Bond lengths/Å178.5(2)N(5)–Pd(1)–N(6)Bond lengths/Å175.6(2)C(11)–Pd(1)–C(21)Bond lengths/ÅDihedral 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/Å40.4(4)N(6)–Pd(1)–C(11)–N(2)Bond lengths/Å39.2(5)N(6)–Pd(1)–C(21)–N(4)Bond lengths/ÅBond lengths/ÅBond lengths/ÅPd(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)Table 3 Crystal data and structure refinement for [{CNC}Pd(C5H4N)][BF4]20626.44Formula weightC20H22B2F8N6Pd0.07 × 0.07 × 0.12Crystal dimensions/mmC20H22B2F8N6PdtriclinicCrystal systemC20H22B2F8N6PdP1̄Space groupC20H22B2F8N6Pd9.8872(5)a/ÅC20H22B2F8N6Pd9.9387(5)b/ÅC20H22B2F8N6Pd12.7418(6)c/ÅC20H22B2F8N6Pd77.790(3)α/°C20H22B2F8N6Pd86.260(3)β/°C20H22B2F8N6Pd85.324(3)γ/°C20H22B2F8N6Pd1218.2(1)V/Å3C20H22B2F8N6Pd2ZC20H22B2F8N6Pd624.00F(000)C20H22B2F8N6Pd183.2T/KC20H22B2F8N6Pd1.708Dc/Mg m−3C20H22B2F8N6Pd0.845μ(Mo-Kα)/mm−1C20H22B2F8N6Pd15462No. collected reflectionsC20H22B2F8N6Pd5578, 0.047No. unique reflections, RintC20H22B2F8N6Pd3701No. of observed reflectionsC20H22B2F8N6Pd334No. of refined parametersC20H22B2F8N6Pd0.049wR(F)C20H22B2F8N6Pd0.041R[I > 3σ(I)]C20H22B2F8N6Pd1.18Goodness-of-fitC20H22B2F8N6Pd0.92, −0.50(Δρ) max, min/e Å−3C20H22B2F8N6PdFormulaC20H22B2F8N6PdFormula weight626.44Crystal dimensions/mm0.07 × 0.07 × 0.12Crystal systemtriclinicSpace groupP1̄a/Å9.8872(5)b/Å9.9387(5)c/Å12.7418(6)α/°77.790(3)β/°86.260(3)γ/°85.324(3)V/Å31218.2(1)Z2F(000)624.00T/K183.2Dc/Mg m−31.708μ(Mo-Kα)/mm−10.845No. collected reflections15462No. unique reflections, Rint5578, 0.047No. of observed reflections3701No. of refined parameters334wR(F)0.049R[I > 3σ(I)]0.041Goodness-of-fit1.18(Δρ) max, min/e Å−30.92, −0.50Table 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)0Bond lengths/ÅBond lengths/Å1Bond lengths/ÅBond lengths/ÅGS(1Br)Bond lengths/ÅBond lengths/Å2Bond lengths/ÅBond lengths/ÅGS(2Br)2.014Pd–E12.017Pd–EGS(1Br)2.066Pd–E22.093Pd–EGS(2Br)2.00Pd–C(11)12.035Pd–C(11)GS(1Br)2.020Pd–C(11)22.034Pd–C(11)GS(2Br)2.5388Pd–Br12.558Pd–BrGS(1Br)2.4250Pd–Br22.422Pd–BrGS(2Br)1.33C(12)–C(13)11.366C(12)–C(13)GS(1Br)1.328C(12)–C(13)21.358C(12)–C(13)GS(2Br)Bond angles/deg.Bond angles/deg.1Bond angles/deg.Bond angles/deg.GS(1Br)Bond angles/deg.Bond angles/deg.2Bond angles/deg.Bond angles/deg.GS(2Br)170.9C(11)–Pd–C(21)1172.2C(11)–Pd–C(21)GS(1Br)173.2C(11)–Pd–C(21)2174.9C(11)–Pd–C(21)GS(2Br)85.1E–Pd–C(11)186.1E–Pd–C(11)GS(1Br)86.7E–Pd–C(11)287.5E–Pd–C(11)GS(2Br)179.6E–Pd–Br1180.0E–Pd–BrGS(1Br)178.9E–Pd–Br2180.0E–Pd–BrGS(2Br)Dihedral angles/deg.Dihedral angles/deg.1Dihedral angles/deg.Dihedral angles/deg.GS(1Br)Dihedral angles/deg.Dihedral angles/deg.2Dihedral angles/deg.Dihedral angles/deg.GS(2Br)42.9C(1)–E–Pd–C(11)141.3C(1)–E–Pd–C(11)GS(1Br)40.6C(1)–E–Pd–C(11)241.0C(1)–E–Pd–C(11)GS(2Br)49.3N(1)–C(7)–C(1)–C(6)152.7N(1)–C(7)–C(1)–C(6)GS(1Br)57.2N(1)–C(7)–C(1)–C(6)256.3N(1)–C(7)–C(1)–C(6)GS(2Br)95.4N(2)–C(11)–C(21)–N(4)196.8N(2)–C(11)–C(21)–N(4)GS(1Br)101.3N(2)–C(11)–C(21)–N(4)291.8N(2)–C(11)–C(21)–N(4)GS(2Br)1GS(1Br)2GS(2Br)Bond lengths/ÅBond lengths/ÅBond lengths/ÅBond lengths/ÅBond lengths/ÅPd–E2.0142.0172.0662.093Pd–C(11)2.002.0352.0202.034Pd–Br2.53882.5582.42502.422C(12)–C(13)1.331.3661.3281.358Bond angles/deg.Bond angles/deg.Bond angles/deg.Bond angles/deg.Bond angles/deg.C(11)–Pd–C(21)170.9172.2173.2174.9E–Pd–C(11)85.186.186.787.5E–Pd–Br179.6180.0178.9180.0Dihedral angles/deg.Dihedral angles/deg.Dihedral angles/deg.Dihedral angles/deg.Dihedral angles/deg.C(1)–E–Pd–C(11)42.941.340.641.0N(1)–C(7)–C(1)–C(6)49.352.757.256.3N(2)–C(11)–C(21)–N(4)95.496.8101.391.8Table 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)02.428Pd–XX = ClGS(1Cl)2.449Pd–XX = ClTS(1Cl)2.445Pd–XX = ClInt(1Cl)2.558Pd–XX = BrGS(1Br)2.595Pd–XX = BrTS(1Br)2.581Pd–XX = BrInt(1Br)2.742Pd–XX = IGS(1I)2.783Pd–XX = ITS(1I)2.774Pd–XX = IInt(1I)2.015Pd–C(6)X = ClGS(1Cl)2.048Pd–C(6)X = ClTS(1Cl)2.055Pd–C(6)X = ClInt(1Cl)2.018Pd–C(6)X = BrGS(1Br)2.049Pd–C(6)X = BrTS(1Br)2.060Pd–C(6)X = BrInt(1Br)2.020Pd–C(6)X = IGS(1I)2.056Pd–C(6)X = ITS(1I)2.065Pd–C(6)X = IInt(1I)2.034Pd–C(11)X = ClGS(1Cl)2.016Pd–C(11)X = ClTS(1Cl)2.042Pd–C(11)X = ClInt(1Cl)2.035Pd–C(11)X = BrGS(1Br)2.012Pd–C(11)X = BrTS(1Br)2.037Pd–C(11)X = BrInt(1Br)2.034Pd–C(11)X = IGS(1I)2.015Pd–C(11)X = ITS(1I)2.034Pd–C(11)X = IInt(1I)2.034Pd–C(21)X = ClGS(1Cl)2.067Pd–C(21)X = ClTS(1Cl)2.042Pd–C(21)X = ClInt(1Cl)2.035Pd–C(21)X = BrGS(1Br)2.067Pd–C(21)X = BrTS(1Br)2.040Pd–C(21)X = BrInt(1Br)2.034Pd–C(21)X = IGS(1I)2.055Pd–C(21)X = ITS(1I)2.034Pd–C(21)X = IInt(1I)180.0C(6)–Pd–XX = ClGS(1Cl)158.9C(6)–Pd–XX = ClTS(1Cl)159.4C(6)–Pd–XX = ClInt(1Cl)180.0C(6)–Pd–XX = BrGS(1Br)154.9C(6)–Pd–XX = BrTS(1Br)156.2C(6)–Pd–XX = BrInt(1Br)180.0C(6)–Pd–XX = IGS(1I)151.6C(6)–Pd–XX = ITS(1I)151.6C(6)–Pd–XX = IInt(1I)173.2C(11)–Pd–C(21)X = ClGS(1Cl)159.6C(11)–Pd–C(21)X = ClTS(1Cl)157.3C(11)–Pd–C(21)X = ClInt(1Cl)172.2C(11)–Pd–C(21)X = BrGS(1Br)159.6C(11)–Pd–C(21)X = BrTS(1Br)156.5C(11)–Pd–C(21)X = BrInt(1Br)171.5C(11)–Pd–C(21)X = IGS(1I)158.7C(11)–Pd–C(21)X = ITS(1I)156.0C(11)–Pd–C(21)X = IInt(1I)−52.2C(6)–C(1)–C(7)–N(1)X = ClGS(1Cl)−54.8C(6)–C(1)–C(7)–N(1)X = ClTS(1Cl)−49.6C(6)–C(1)–C(7)–N(1)X = ClInt(1Cl)−52.7C(6)–C(1)–C(7)–N(1)X = BrGS(1Br)−54.9C(6)–C(1)–C(7)–N(1)X = BrTS(1Br)−50.5C(6)–C(1)–C(7)–N(1)X = BrInt(1Br)−52.9C(6)–C(1)–C(7)–N(1)X = IGS(1I)−55.1C(6)–C(1)–C(7)–N(1)X = ITS(1I)−49.2C(6)–C(1)–C(7)–N(1)X = IInt(1I)−52.2C(6)–C(5)–C(8)–N(3)X = ClGS(1Cl)33.2C(6)–C(5)–C(8)–N(3)X = ClTS(1Cl)49.7C(6)–C(5)–C(8)–N(3)X = ClInt(1Cl)−52.7C(6)–C(5)–C(8)–N(3)X = BrGS(1Br)27.6C(6)–C(5)–C(8)–N(3)X = BrTS(1Br)49.1C(6)–C(5)–C(8)–N(3)X = BrInt(1Br)−52.9C(6)–C(5)–C(8)–N(3)X = IGS(1I)27.2C(6)–C(5)–C(8)–N(3)X = ITS(1I)49.2C(6)–C(5)–C(8)–N(3)X = IInt(1I)X = ClX = ClX = ClX = BrX = BrX = BrX = IX = IX = IGS(1Cl)TS(1Cl)Int(1Cl)GS(1Br)TS(1Br)Int(1Br)GS(1I)TS(1I)Int(1I)Pd–X2.4282.4492.4452.5582.5952.5812.7422.7832.774Pd–C(6)2.0152.0482.0552.0182.0492.0602.0202.0562.065Pd–C(11)2.0342.0162.0422.0352.0122.0372.0342.0152.034Pd–C(21)2.0342.0672.0422.0352.0672.0402.0342.0552.034C(6)–Pd–X180.0158.9159.4180.0154.9156.2180.0151.6151.6C(11)–Pd–C(21)173.2159.6157.3172.2159.6156.5171.5158.7156.0C(6)–C(1)–C(7)–N(1)−52.2−54.8−49.6−52.7−54.9−50.5−52.9−55.1−49.2C(6)–C(5)–C(8)–N(3)−52.233.249.7−52.727.649.1−52.927.249.202.294Pd–XGS(2Cl)2.300Pd–XTS(2Cl)2.308Pd–XInt(2Cl)2.422Pd–XGS(2Br)2.436Pd–XTS(2Br)2.437Pd–XInt(2Br)2.607Pd–XGS(2I)2.630Pd–XTS(2I)2.626Pd–XInt(2I)2.081Pd–N(5)GS(2Cl)2.159Pd–N(5)TS(2Cl)2.174Pd–N(5)Int(2Cl)2.093Pd–N(5)GS(2Br)2.167Pd–N(5)TS(2Br)2.193Pd–N(5)Int(2Br)2.104Pd–N(5)GS(2I)2.182Pd–N(5)TS(2I)2.226Pd–N(5)Int(2I)2.031Pd–C(11)GS(2Cl)2.029Pd–C(11)TS(2Cl)2.046Pd–C(11)Int(2Cl)2.034Pd–C(11)GS(2Br)2.021Pd–C(11)TS(2Br)2.046Pd–C(11)Int(2Br)2.037Pd–C(11)GS(2I)2.013Pd–C(11)TS(2I)2.035Pd–C(11)Int(2I)2.031Pd–C(21)GS(2Cl)2.064Pd–C(21)TS(2Cl)2.046Pd–C(21)Int(2Cl)2.034Pd–C(21)GS(2Br)2.068Pd–C(21)TS(2Br)2.037Pd–C(21)Int(2Br)2.037Pd–C(21)GS(2I)2.067Pd–C(21)TS(2I)2.035Pd–C(21)Int(2I)180.0N(5)–Pd-XGS(2Cl)162.3N(5)–Pd-XTS(2Cl)158.6N(5)–Pd-XInt(2Cl)180.0N(5)–Pd-XGS(2Br)158.8N(5)–Pd-XTS(2Br)155.1N(5)–Pd-XInt(2Br)180.0N(5)–Pd-XGS(2I)153.5N(5)–Pd-XTS(2I)147.9N(5)–Pd-XInt(2I)175.8C(11)–Pd–C(21)GS(2Cl)163.6C(11)–Pd–C(21)TS(2Cl)161.0C(11)–Pd–C(21)Int(2Cl)174.9C(11)–Pd–C(21)GS(2Br)163.8C(11)–Pd–C(21)TS(2Br)161.1C(11)–Pd–C(21)Int(2Br)173.8C(11)–Pd–C(21)GS(2I)164.1C(11)–Pd–C(21)TS(2I)160.8C(11)–Pd–C(21)Int(2I)−55.9N(5)–C(1)–C(7)–N(1)GS(2Cl)−66.5N(5)–C(1)–C(7)–N(1)TS(2Cl)−61.3N(5)–C(1)–C(7)–N(1)Int(2Cl)−56.4N(5)–C(1)–C(7)–N(1)GS(2Br)−67.2N(5)–C(1)–C(7)–N(1)TS(2Br)−61.2N(5)–C(1)–C(7)–N(1)Int(2Br)−56.9N(5)–C(1)–C(7)–N(1)GS(2I)−66.4N(5)–C(1)–C(7)–N(1)TS(2I)−60.9N(5)–C(1)–C(7)–N(1)Int(2I)−55.9N(5)–C(5)–C(8)–N(3)GS(2Cl)50.9N(5)–C(5)–C(8)–N(3)TS(2Cl)61.3N(5)–C(5)–C(8)–N(3)Int(2Cl)−56.4N(5)–C(5)–C(8)–N(3)GS(2Br)43.6N(5)–C(5)–C(8)–N(3)TS(2Br)61.7N(5)–C(5)–C(8)–N(3)Int(2Br)−56.9N(5)–C(5)–C(8)–N(3)GS(2I)33.2N(5)–C(5)–C(8)–N(3)TS(2I)60.9N(5)–C(5)–C(8)–N(3)Int(2I)GS(2Cl)TS(2Cl)Int(2Cl)GS(2Br)TS(2Br)Int(2Br)GS(2I)TS(2I)Int(2I)Pd–X2.2942.3002.3082.4222.4362.4372.6072.6302.626Pd–N(5)2.0812.1592.1742.0932.1672.1932.1042.1822.226Pd–C(11)2.0312.0292.0462.0342.0212.0462.0372.0132.035Pd–C(21)2.0312.0642.0462.0342.0682.0372.0372.0672.035N(5)–Pd-X180.0162.3158.6180.0158.8155.1180.0153.5147.9C(11)–Pd–C(21)175.8163.6161.0174.9163.8161.1173.8164.1160.8N(5)–C(1)–C(7)–N(1)−55.9−66.5−61.3−56.4−67.2−61.2−56.9−66.4−60.9N(5)–C(5)–C(8)–N(3)−55.950.961.3−56.443.661.7−56.933.260.9Table 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 geometries069.9X = Cl[{CCC}PdX]ΔE†GP69.5X = Cl[{CCC}PdX]ΔE†PCM68.0X = Cl[{CCC}PdX]ΔEGP68.9X = Cl[{CCC}PdX]ΔEPCM73.2X = Cl[{CNC}PdX]+ΔE†GP75.5X = Cl[{CNC}PdX]+ΔE†PCM74.9X = Cl[{CNC}PdX]+ΔEGP71.8X = Cl[{CNC}PdX]+ΔEPCM71.4X = Br[{CCC}PdX]ΔE†GP72.3X = Br[{CCC}PdX]ΔE†PCM68.2X = Br[{CCC}PdX]ΔEGP71.2X = Br[{CCC}PdX]ΔEPCM73.0X = Br[{CNC}PdX]+ΔE†GP75.3X = Br[{CNC}PdX]+ΔE†PCM72.3X = Br[{CNC}PdX]+ΔEGP66.6X = Br[{CNC}PdX]+ΔEPCM72.5X = I[{CCC}PdX]ΔE†GP72.4X = I[{CCC}PdX]ΔE†PCM69.0X = I[{CCC}PdX]ΔEGP66.5X = I[{CCC}PdX]ΔEPCM72.9X = I[{CNC}PdX]+ΔE†GP79.3X = I[{CNC}PdX]+ΔE†PCM69.7X = I[{CNC}PdX]+ΔEGP67.2X = I[{CNC}PdX]+ΔEPCM[{CCC}PdX][{CCC}PdX][{CCC}PdX][{CCC}PdX][{CNC}PdX]+[{CNC}PdX]+[{CNC}PdX]+[{CNC}PdX]+ΔE†ΔE†ΔEΔEΔE†ΔE†ΔEΔEGPPCMGPPCMGPPCMGPPCMX = Cl69.969.568.068.973.275.574.971.8X = Br71.472.368.271.273.075.372.366.6X = I72.572.469.066.572.979.369.767.2Table 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)02.390Pd–XX = ClGS(2Cl2)2.367Pd–XX = ClTS(2Cl2)2.370Pd–XX = ClInt(2Cl2)2.531Pd–XX = BrGS(2Br2)2.503Pd–XX = BrTS(2Br2)2.505Pd–XX = BrInt(2Br2)2.730Pd–XX = IGS(2I2)2.695Pd–XX = ITS(2I2)2.695Pd–XX = IInt(2I2)2.578Pd–N(5)X = ClGS(2Cl2)2.657Pd–N(5)X = ClTS(2Cl2)2.753Pd–N(5)X = ClInt(2Cl2)2.554Pd–N(5)X = BrGS(2Br2)2.635Pd–N(5)X = BrTS(2Br2)2.735Pd–N(5)X = BrInt(2Br2)2.525Pd–N(5)X = IGS(2I2)2.605Pd–N(5)X = ITS(2I2)2.713Pd–N(5)X = IInt(2I2)2.015Pd–C(11)X = ClGS(2Cl2)2.016Pd–C(11)X = ClTS(2Cl2)2.023Pd–C(11)X = ClInt(2Cl2)2.015Pd–C(11)X = BrGS(2Br2)2.015Pd–C(11)X = BrTS(2Br2)2.021Pd–C(11)X = BrInt(2Br2)2.017Pd–C(11)X = IGS(2I2)2.016Pd–C(11)X = ITS(2I2)2.022Pd–C(11)X = IInt(2I2)2.023Pd–C(21)X = ClGS(2Cl2)2.021Pd–C(21)X = ClTS(2Cl2)2.022Pd–C(21)X = ClInt(2Cl2)2.020Pd–C(21)X = BrGS(2Br2)2.020Pd–C(21)X = BrTS(2Br2)2.021Pd–C(21)X = BrInt(2Br2)2.018Pd–C(21)X = IGS(2I2)2.018Pd–C(21)X = ITS(2I2)2.022Pd–C(21)X = IInt(2I2)94.4N(5)–Pd–XX = ClGS(2Cl2)93.9N(5)–Pd–XX = ClTS(2Cl2)99.0N(5)–Pd–XX = ClInt(2Cl2)96.3N(5)–Pd–XX = BrGS(2Br2)94.2N(5)–Pd–XX = BrTS(2Br2)99.3N(5)–Pd–XX = BrInt(2Br2)98.7N(5)–Pd–XX = IGS(2I2)94.9N(5)–Pd–XX = ITS(2I2)100.2N(5)–Pd–XX = IInt(2I2)85.4N(5)–Pd–C(11)X = ClGS(2Cl2)90.7N(5)–Pd–C(11)X = ClTS(2Cl2)88.1N(5)–Pd–C(11)X = ClInt(2Cl2)85.3N(5)–Pd–C(11)X = BrGS(2Br2)90.5N(5)–Pd–C(11)X = BrTS(2Br2)88.3N(5)–Pd–C(11)X = BrInt(2Br2)86.0N(5)–Pd–C(11)X = IGS(2I2)90.5N(5)–Pd–C(11)X = ITS(2I2)88.5N(5)–Pd–C(11)X = IInt(2I2)168.6C(11)–Pd–C(21)X = ClGS(2Cl2)172.0C(11)–Pd–C(21)X = ClTS(2Cl2)175.4C(11)–Pd–C(21)X = ClInt(2Cl2)169.9C(11)–Pd–C(21)X = BrGS(2Br2)172.3C(11)–Pd–C(21)X = BrTS(2Br2)176.1C(11)–Pd–C(21)X = BrInt(2Br2)171.9C(11)–Pd–C(21)X = IGS(2I2)173.2C(11)–Pd–C(21)X = ITS(2I2)176.5C(11)–Pd–C(21)X = IInt(2I2)−63.1N(5)–C(1)–C(7)–N(1)X = ClGS(2Cl2)−94.4N(5)–C(1)–C(7)–N(1)X = ClTS(2Cl2)−93.1N(5)–C(1)–C(7)–N(1)X = ClInt(2Cl2)−56.9N(5)–C(1)–C(7)–N(1)X = BrGS(2Br2)−91.3N(5)–C(1)–C(7)–N(1)X = BrTS(2Br2)−92.3N(5)–C(1)–C(7)–N(1)X = BrInt(2Br2)−53.2N(5)–C(1)–C(7)–N(1)X = IGS(2I2)−87.4N(5)–C(1)–C(7)–N(1)X = ITS(2I2)−90.7N(5)–C(1)–C(7)–N(1)X = IInt(2I2)−47.0N(5)–C(5)–C(8)–N(3)X = ClGS(2Cl2)31.1N(5)–C(5)–C(8)–N(3)X = ClTS(2Cl2)93.2N(5)–C(5)–C(8)–N(3)X = ClInt(2Cl2)−51.6N(5)–C(5)–C(8)–N(3)X = BrGS(2Br2)24.8N(5)–C(5)–C(8)–N(3)X = BrTS(2Br2)92.3N(5)–C(5)–C(8)–N(3)X = BrInt(2Br2)−53.0N(5)–C(5)–C(8)–N(3)X = IGS(2I2)19.2N(5)–C(5)–C(8)–N(3)X = ITS(2I2)90.7N(5)–C(5)–C(8)–N(3)X = IInt(2I2)X = ClX = ClX = ClX = BrX = BrX = BrX = IX = IX = IGS(2Cl2)TS(2Cl2)Int(2Cl2)GS(2Br2)TS(2Br2)Int(2Br2)GS(2I2)TS(2I2)Int(2I2)Pd–X2.3902.3672.3702.5312.5032.5052.7302.6952.695Pd–N(5)2.5782.6572.7532.5542.6352.7352.5252.6052.713Pd–C(11)2.0152.0162.0232.0152.0152.0212.0172.0162.022Pd–C(21)2.0232.0212.0222.0202.0202.0212.0182.0182.022N(5)–Pd–X94.493.999.096.394.299.398.794.9100.2N(5)–Pd–C(11)85.490.788.185.390.588.386.090.588.5C(11)–Pd–C(21)168.6172.0175.4169.9172.3176.1171.9173.2176.5N(5)–C(1)–C(7)–N(1)−63.1−94.4−93.1−56.9−91.3−92.3−53.2−87.4−90.7N(5)–C(5)–C(8)–N(3)−47.031.193.2−51.624.892.3−53.019.290.7Table 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 geometries011.2X = ClΔE†GP10.4X = ClΔE†PCM0.2X = ClΔEGP0.8X = ClΔEPCM10.3X = BrΔE†GP11.9X = BrΔE†PCM−4.1X = BrΔEGP−1.4X = BrΔEPCM10.1X = IΔE†GP12.8X = IΔE†PCM−8.0X = IΔEGP−3.0X = IΔEPCMΔE†ΔE†ΔEΔEGPPCMGPPCMX = Cl11.210.40.20.8X = Br10.311.9−4.1−1.4X = I10.112.8−8.0−3.0http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-f1.gifX-Ray structure of the pyridine complex.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-f2.gifOptimized geometry for Pd{CCC}Br, GS(1Br), and Pd{CNC}Br+, GS(2Br), at the B3PW91 level.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-f3.gifMechanism for interconversion for Pd{CCC}Br. Energies are in kJ mol−1.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-s1.gifhttp://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-f4.gifMechanism for interconversion for Pd{CNC}2+. Energies are in kJ mol−1.http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-f5.gifMechanism for interconversion for [Pd{CNC}(Br)2]. Energies are in kJ mol−1.(10^6.0) * Gram^(1.0) Meter^(-3.0)1.708C20H22B2F8N6PdMgm−31.708DcC20H22B2F8N6PdNFPdCHBsystemAutoTableParsertriclinicC20H22B2F8N6PdCrystal system0.1Angstrom^(3.0)1218.2C20H22B2F8N6PdÅ31218.2(1)VP1̄C20H22B2F8N6PdSpace group0.0005Angstrom^(1.0)9.8872C20H22B2F8N6PdÅ9.8872(5)a0.0005Angstrom^(1.0)9.9387C20H22B2F8N6PdÅ9.9387(5)b0.0006000000000000001Angstrom^(1.0)12.7418C20H22B2F8N6PdÅ12.7418(6)c0.003Degrees^(1.0)86.26C20H22B2F8N6Pd°86.260(3)β0.003Degrees^(1.0)77.79C20H22B2F8N6Pd°77.790(3)α0.003Degrees^(1.0)85.324C20H22B2F8N6Pd°85.324(3)γFalse2.0C20H22B2F8N6Pd2ZC20H22B2F8N6PdCrystal system624.0C20H22B2F8N6Pd624.00F(000)Kelvin^(1.0)183.2C20H22B2F8N6PdK183.2T(10^3.0) * Meter^(-1.0)0.845C20H22B2F8N6Pdmm−10.845μ(Mo-Kα)626.44C20H22B2F8N6Pd626.44Formula weightC20H22B2F8N6PdNFPdCHBSpace groupAutoTableParsertriclinicC20H22B2F8N6PdCrystal system0.1Angstrom^(3.0)1218.2C20H22B2F8N6PdÅ31218.2(1)VP1̄C20H22B2F8N6PdSpace group0.0005Angstrom^(1.0)9.8872C20H22B2F8N6PdÅ9.8872(5)a0.0005Angstrom^(1.0)9.9387C20H22B2F8N6PdÅ9.9387(5)b0.0006000000000000001Angstrom^(1.0)12.7418C20H22B2F8N6PdÅ12.7418(6)c0.003Degrees^(1.0)86.26C20H22B2F8N6Pd°86.260(3)β0.003Degrees^(1.0)77.79C20H22B2F8N6Pd°77.790(3)α0.003Degrees^(1.0)85.324C20H22B2F8N6Pd°85.324(3)γFalse2.0C20H22B2F8N6Pd2ZC20H22B2F8N6PdSpace group624.0C20H22B2F8N6Pd624.00F(000)Kelvin^(1.0)183.2C20H22B2F8N6PdK183.2T(10^3.0) * Meter^(-1.0)0.845C20H22B2F8N6Pdmm−10.845μ(Mo-Kα)626.44C20H22B2F8N6Pd626.44Formula weight10.1039/b210784hhalideacetoneC(21)–Pd–BrCortho1H1HNCH2CH2CH2CH3CH3-ChalideBr1-butylimidazolehalidehalidesNCH2CH2CH2CH3Nimidazole2HC(11)–Pd–C(21)CNCDMSO-d6ClpyridineNCH2CH2CH2CH3tridentate(η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)chloropalladium(II)(1+) tosylateBr1HCH2BrNCH3BrClDMSOhalideCH2Cl2/pentane2Htosylatepy-CH2-NPd1HEt2OCHCl32HpyridineCltosylateH3C-C-(CH)2NCH32,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}phenylcarbenes2H13C{1H}[{CNC}Pd(C5H5N)][BF4]2NCH2CH2CH2CH32HCH3BrNCH3[{CNC}Pd(solvent)](BF4)2tosylate-HDMSO2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}phenyl)bromopalladium(IINCH2CH2CH2CH3(η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)aquapalladium(II)(2+) fluoroborateNCH2CH2CH2CH3DMSONCH3CNCacetone2HBrPd{CCC}Br{CCC}Pd(XIS)Pd–C(11)ClPd{CCC}Br1HDMSO-d61HC22H24N5IO3PdS·H2O−20 °ChalidesPd{CNC}Br+pyCH2N13C{1H}PdNCH2CH2CH2CH3DMSO-d6HNCH3odile.eisensteinNCH32HPdPdC(6)–Pd–BrH3C-C-(CH)2CNC1HDMSO-d6Br1HCorthodiethyl etherDMSO-d6HpyridineNCH3NHNCH2CH2CH2CH32HBrBrη3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridineBr1Haryl C(6)HCHCl3AgOTsBr2HhalideiodideBr13C{1H}diethyl etherSiMe4ClNCH3Cl2HNCelitepyridinepyridine{CNC′}22HClCNCCl(η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)bromopalladium(II)(1+) tosylatepyridinePd pincerCH3d6-dmsopyCH2NEtOHtosylate-HNaOTsCH2Cl2NNhalideHCelitemethylCH2Cl2/Et2ONaOTs2HC(6)–Pd–Brhalide2Hpyridine2Br−tosylate-H2Hmethylmethyl(η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)iodopalladium(II)(1+) iodideNCHN4-coordinateCNCPd{CEC}Br, GS(1Br) (E = C){CNC}PdX2PdNaOTsbromideCl[{CNC}PdCl]ClNCH3CH22HPd(1)–N(5)Br[{CNC}PdBr]Br2H2H[{CNC}Pd(OH2)]+py-CH2-N{CNC}Pd(XIS)][XOSpyridinetosylate-HmethylPd(OAc)2methanol/Et2OhalidepyridinepyCH2Nmethylmethylpy-CH2-NAgBF413C{1H}C-CH3PdiodidepyCH2N2HPd–N(5)Mepyridined6-dmsochloroXOSpy-CH2N1,4-dioxanepyridine N(5)13C{1H}2,6-bis(bromomethyl)pyridinePdCortho(η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)iodopalladium(II)(1+) tosylateCH3(η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)pyridinepalladium(II)(2+) fluoroborateCHCl31H2HBrarylNCH2CH2CH2CH3HDMSOCHCl3methanolhalideC(11)–Pd–C(21)acetoneH3C-C-(CH)2bromidePd–N(5)CH3-CN-methyl1HCortho2HNCNCPd{CEC}BrBrBrCH2Cl21,4-dioxanePdpyCH2NCNCacetone/Et2O[{CNC}PdX]+Et2OPd–C(11)–N(2)pyCH2NBrPd⋯C(14)(η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)chloropalladium(II)(1+) chlorideC-CH3Pd(OAc)2acetoneCD2Cl2CH2Cl22HNCH2CH2CH2CH3py-CH2-N2H1HCH2Cl2py-CH2-NhalideHydrogenPd–C(6)CorthoPdDMSONCHHCH2CH2CH3Pdpyridinehydrogen2HNCH3ClGS(1Br)HPd(II)hydrogenClhalide(η3-C,C′,N)(2,6-Bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)bromopalladium(II)(1+) bromide1H1HBrCH2NCHHCH2CH2CH31Hpy-CH2N2HcarbeneHCHCl3[{CNC}Pd(C5H5N)](BF4)21-methylimidazole13C{1H}1HN(4)C(11)–Pd–C(21)pyridineIodidePd{CNC}2+AgBF4Hacetone2H1Hn-Bupyridinetosylate-H13C{1H}NCH2CH2CH2CH31,4-dioxanemethanoln-BuBrNCH3NPdPdhalideBrhalidePd–BrPdCNCmethanol2HEt2OpyCH2NEt2OhalideNaI2HCedexDMSO-d6Pd–C(6)GS(1Br)1,4-dioxaneCelitePd–C(6)HpalladiumBrCINES2H2HpyridineNCH32HacetoneNCH2CH2CH2CH3tosylate-H13C{1H}methanolPdR = Mecarbene1HEt2O2HAgOTsC15H17N5Cl2Pd1·1H2Omethyl[{CNC}PdX]+CH21Hacetonepyridine NDMSO-d6DMSONCH2CH2CH2CH3H1HhalideNCH3C22H24BrN5O3PdS·CH3OH2H2,6-bis(chloromethyl)pyridine2HDMSO-d62HpyCH2NBrN2HHPd–C(21)ClpyridineNCH3[(CNC)Pd(py)](BF4)2pyridineClDMSO-d6pyridineNCH32HhalidesC21H29Br2N5Pd2H2H2HHPd–BrC(6)CelitemethylDMSO-d62HHmethylmethylNHCNC(6)–Pd–C(21)13C{1H}CH3-CNcarbonsη3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)bromopalladium(II)(1+CH2 HPd{CNC}BrC(11)–Pd–C(21)ClhalidehalideNaIC-CH3chlorideNCH3pyCH2NCelitehalidesH2HhalideN1H(627.56)·0.5EtOHNmethanol/Et2Omethyleneacetone/Et2O2H2HNmethyl13C{1H}50John R. MiecznikowskiStephan GründemannMartin AlbrechtClaire MégretEric ClotJack W. FallerOdile EisensteinRobert H. CrabtreeJohn R. MiecznikowskiStephan GründemannMartin AlbrechtClaire MégretEric ClotJack W. FallerOdile EisensteinRobert H. CrabtreeDalton Transactionshttp://pubs.rsc.org/en/Content/ArticlePDF/2003/DT/B210784Hhttp://pubs.rsc.org/en/Content/ArticleLanding/2003/DT/B210784H838831Royal Society of Chemistry127CCCNN=JJ(-LRB-η3-C,C′,C″NN)-RRB-η3-C,C′,C″CCC =2320=JJ(η3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)B-CM)-RRB-(η3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)=2219pincerNN(-LRB-TableNNTablepincer3228intermediateJJInt(1X)NN(-LRB-TableNNTableintermediate Int(1X)51activationNNenergyNN(-LRB-ΔENNΔEactivation energy2825experimentNN(-LRB-ΔGNNΔGexperiment62activationNNenergyNN(-LRB-TableNNTableactivation energy1613TSNN(-LRB-TableNNTableTS4137energyNNpatternNN(-LRB-TableNNTableenergy pattern51transitionNNstateNN,,TS(2□)NNTS(2□)transition state3632experimentalJJworkNN(-LRB-TableNNTableexperimental work3631neutralJJligandNNXISNN(-LRB-TablesNNSTablesneutral ligand XIS2925CCCNNpincerNN(-LRB-TableNNTableCCC pincer5349bondNNdistanceNN(-LRB-TableNNTablebond distance1310INN(-LRB-TableNNTableI3229GS(2X2)NN(-LRB-TableNNTableGS(2X2)1511energyNNpatternNN(-LRB-TableNNTableenergy pattern4237fJJpolarizationNNfunctionNN(-LRB-αNNαf polarization function2419polarizationNNdNNfunctionNN(-LRB-αNNαpolarization d function95NoniusJJKappaCCDNN(-LRB-Mo-KαNNMo-KαNonius KappaCCD1814absorptionNN(-LRB-SORTAVNN)-RRB-SORTAVabsorption41NMRNNP::δNNδNMR41NMRNNP::δNNδNMR41NMRNNP::δNNδNMR41NMRNNP::δNNδNMR41NMRNNP::δNNδNMR41NMRNNP::δNNδNMR41NMRNNP::δNNδNMR121118NMRNNP::δNNδNMR41NMRNNP::δNNδNMR41NMRNNP::δNNδNMR2003-02-24( η3-C,C′,C″CCC(η3-C,C′,N)(2,6-bis{[N-methyl-N′-methylene]imidazol-2-ylidene}pyridine)CNC−35.5(3) ° and N(5) – Pd(1)N(1)−41.1(3) ° and C(11)C(1)potential energy surfacePESrelativistic effective core potentialRECPdistortionless enhancement of polarization transferDEPTS ) , 141.66 ( Cpara ) , 137.46 ( C-CH3 ) , 127.96S-C-(CH)2C-S ) , 141.78 ( Cpara ) , 137.64 ( C-CH3 ) , 128.09S-C-(CH)2S-C ) , 142.12 ( Cpara ) , 137.86 ( C-CH3 ) , 128.38S-C-(CH)2