{ "job_id": "0063c283-59fd-4d72-a5eb-4f9475000726", "created_at": "2020-06-24T12:52:04.202395", "status": "SUCCESS", "result": [ { "biblio": { "filename": "0063c283-59fd-4d72-a5eb-4f9475000726.html" }, "tables": [ { "caption": "Table 1 Data on the fluxionality", "heading": 0, "tde_table": [ [ "[{CCC}PdBr]", [ "1" ], [ "Complex" ] ], [ "350", [ "1" ], [ "T(coal.)/K" ] ], [ "70.9", [ "1" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "d6-dmso", [ "1" ], [ "Solvent" ] ], [ "[{CNC}PdCl]Cl", [ "2" ], [ "Complex" ] ], [ "308", [ "2" ], [ "T(coal.)/K" ] ], [ "59.3", [ "2" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "CDCl3", [ "2" ], [ "Solvent" ] ], [ "[{CNC}PdCl]OTs", [ "3" ], [ "Complex" ] ], [ "343", [ "3" ], [ "T(coal.)/K" ] ], [ "66.0", [ "3" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "d6-dmso", [ "3" ], [ "Solvent" ] ], [ "[{CNC}PdBr]Br", [ "4" ], [ "Complex" ] ], [ "278", [ "4" ], [ "T(coal.)/K" ] ], [ "52.9", [ "4" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "CDCl3", [ "4" ], [ "Solvent" ] ], [ "[{CNC}PdBr]OTs", [ "5" ], [ "Complex" ] ], [ "373", [ "5" ], [ "T(coal.)/K" ] ], [ "77.6", [ "5" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "d6-dmso", [ "5" ], [ "Solvent" ] ], [ "[{CNC}PdI]I", [ "6" ], [ "Complex" ] ], [ "208", [ "6" ], [ "T(coal.)/K" ] ], [ "41.9", [ "6" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "CD2Cl2", [ "6" ], [ "Solvent" ] ], [ "[{CNC}PdI]OTs", [ "7" ], [ "Complex" ] ], [ "338", [ "7" ], [ "T(coal.)/K" ] ], [ "70.9", [ "7" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "d6-dmso", [ "7" ], [ "Solvent" ] ], [ "[{CNC}Pd(OH2)][BF4]2", [ "8" ], [ "Complex" ] ], [ ">353", [ "8" ], [ "T(coal.)/K" ] ], [ ">73", [ "8" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "CDCl3", [ "8" ], [ "Solvent" ] ], [ "[{CNC}PdCl]Cl", [ "9" ], [ "Complex" ] ], [ "303", [ "9" ], [ "T(coal.)/K" ] ], [ "60.0", [ "9" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "CD2Cl2", [ "9" ], [ "Solvent" ] ], [ "[{CNC}Pd(py)][BF4]2", [ "10" ], [ "Complex" ] ], [ ">403", [ "10" ], [ "T(coal.)/K" ] ], [ ">73", [ "10" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "d6-dmso", [ "10" ], [ "Solvent" ] ], [ "[{CNC\u2032}PdBr]Br", [ "11" ], [ "Complex" ] ], [ "303", [ "11" ], [ "T(coal.)/K" ] ], [ "57.4", [ "11" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "CDCl3", [ "11" ], [ "Solvent" ] ], [ "[{CNC}Pd(OH2)][BF4]2", [ "12" ], [ "Complex" ] ], [ "343", [ "12" ], [ "T(coal.)/K" ] ], [ "68.5", [ "12" ], [ "\u0394G\u2020/kJ mol\u22121" ] ], [ "d6-dmso", [ "12" ], [ "Solvent" ] ] ], "tde_raw_table": [ [ "Entry", "Complex", "T(coal.)/K", "\u0394G\u2020/kJ mol\u22121", "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", ">353", ">73", "CDCl3" ], [ "9", "[{CNC}PdCl]Cl", "303", "60.0", "CD2Cl2" ], [ "10", "[{CNC}Pd(py)][BF4]2", ">403", ">73", "d6-dmso" ], [ "11", "[{CNC\u2032}PdBr]Br", "303", "57.4", "CDCl3" ], [ "12", "[{CNC}Pd(OH2)][BF4]2", "343", "68.5", "d6-dmso" ] ] }, { "caption": "Table 2 Selected bond lengths and angles for complex [{CNC}Pd(C5H4N)][BF4]2", "heading": 0, "tde_table": [ [ "2.060(4)", [ "Pd(1)\u2013N(5)" ], [ "Bond lengths/\u00c5" ] ], [ "2.017(4)", [ "Pd(1)\u2013N(6)" ], [ "Bond lengths/\u00c5" ] ], [ "2.021(4)", [ "Pd(1)\u2013C(11)" ], [ "Bond lengths/\u00c5" ] ], [ "2.027(4)", [ "Pd(1)\u2013C(21)" ], [ "Bond lengths/\u00c5" ] ], [ "Bond angles/deg.", [ "Bond angles/deg." ], [ "Bond lengths/\u00c5" ] ], [ "87.8(2)", [ "N(5)\u2013Pd(1)\u2013C(11)" ], [ "Bond lengths/\u00c5" ] ], [ "88.4(2)", [ "N(5)\u2013Pd(1)\u2013C(21)" ], [ "Bond lengths/\u00c5" ] ], [ "92.1(2)", [ "N(6)\u2013Pd(1)\u2013C(11)" ], [ "Bond lengths/\u00c5" ] ], [ "91.8(2)", [ "N(6)\u2013Pd(1)\u2013C(21)" ], [ "Bond lengths/\u00c5" ] ], [ "178.5(2)", [ "N(5)\u2013Pd(1)\u2013N(6)" ], [ "Bond lengths/\u00c5" ] ], [ "175.6(2)", [ "C(11)\u2013Pd(1)\u2013C(21)" ], [ "Bond lengths/\u00c5" ] ], [ "Dihedral angles/deg.", [ "Dihedral angles/deg." ], [ "Bond lengths/\u00c5" ] ], [ "\u221241.1(3)", [ "C(11)\u2013Pd(1)\u2013N(5)\u2013C(1)" ], [ "Bond lengths/\u00c5" ] ], [ "\u221265.1(3)", [ "C(11)\u2013Pd(1)\u2013N(6)\u2013C(1)" ], [ "Bond lengths/\u00c5" ] ], [ "40.4(4)", [ "N(6)\u2013Pd(1)\u2013C(11)\u2013N(2)" ], [ "Bond lengths/\u00c5" ] ], [ "39.2(5)", [ "N(6)\u2013Pd(1)\u2013C(21)\u2013N(4)" ], [ "Bond lengths/\u00c5" ] ] ], "tde_raw_table": [ [ "Bond lengths/\u00c5", "Bond lengths/\u00c5" ], [ "Pd(1)\u2013N(5)", "2.060(4)" ], [ "Pd(1)\u2013N(6)", "2.017(4)" ], [ "Pd(1)\u2013C(11)", "2.021(4)" ], [ "Pd(1)\u2013C(21)", "2.027(4)" ], [ "Bond angles/deg.", "Bond angles/deg." ], [ "N(5)\u2013Pd(1)\u2013C(11)", "87.8(2)" ], [ "N(5)\u2013Pd(1)\u2013C(21)", "88.4(2)" ], [ "N(6)\u2013Pd(1)\u2013C(11)", "92.1(2)" ], [ "N(6)\u2013Pd(1)\u2013C(21)", "91.8(2)" ], [ "N(5)\u2013Pd(1)\u2013N(6)", "178.5(2)" ], [ "C(11)\u2013Pd(1)\u2013C(21)", "175.6(2)" ], [ "Dihedral angles/deg.", "Dihedral angles/deg." ], [ "C(11)\u2013Pd(1)\u2013N(5)\u2013C(1)", "\u221241.1(3)" ], [ "C(11)\u2013Pd(1)\u2013N(6)\u2013C(1)", "\u221265.1(3)" ], [ "N(6)\u2013Pd(1)\u2013C(11)\u2013N(2)", "40.4(4)" ], [ "N(6)\u2013Pd(1)\u2013C(21)\u2013N(4)", "39.2(5)" ] ] }, { "caption": "Table 3 Crystal data and structure refinement for [{CNC}Pd(C5H4N)][BF4]2", "heading": 0, "tde_table": [ [ "626.44", [ "Formula weight" ], [ "C20H22B2F8N6Pd" ] ], [ "0.07 \u00d7 0.07 \u00d7 0.12", [ "Crystal dimensions/mm" ], [ "C20H22B2F8N6Pd" ] ], [ "triclinic", [ "Crystal system" ], [ "C20H22B2F8N6Pd" ] ], [ "P1\u0304", [ "Space group" ], [ "C20H22B2F8N6Pd" ] ], [ "9.8872(5)", [ "a/\u00c5" ], [ "C20H22B2F8N6Pd" ] ], [ "9.9387(5)", [ "b/\u00c5" ], [ "C20H22B2F8N6Pd" ] ], [ "12.7418(6)", [ "c/\u00c5" ], [ "C20H22B2F8N6Pd" ] ], [ "77.790(3)", [ "\u03b1/\u00b0" ], [ "C20H22B2F8N6Pd" ] ], [ "86.260(3)", [ "\u03b2/\u00b0" ], [ "C20H22B2F8N6Pd" ] ], [ "85.324(3)", [ "\u03b3/\u00b0" ], [ "C20H22B2F8N6Pd" ] ], [ "1218.2(1)", [ "V/\u00c53" ], [ "C20H22B2F8N6Pd" ] ], [ "2", [ "Z" ], [ "C20H22B2F8N6Pd" ] ], [ "624.00", [ "F(000)" ], [ "C20H22B2F8N6Pd" ] ], [ "183.2", [ "T/K" ], [ "C20H22B2F8N6Pd" ] ], [ "1.708", [ "Dc/Mg m\u22123" ], [ "C20H22B2F8N6Pd" ] ], [ "0.845", [ "\u03bc(Mo-K\u03b1)/mm\u22121" ], [ "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 > 3\u03c3(I)]" ], [ "C20H22B2F8N6Pd" ] ], [ "1.18", [ "Goodness-of-fit" ], [ "C20H22B2F8N6Pd" ] ], [ "0.92, \u22120.50", [ "(\u0394\u03c1) max, min/e \u00c5\u22123" ], [ "C20H22B2F8N6Pd" ] ] ], "tde_raw_table": [ [ "Formula", "C20H22B2F8N6Pd" ], [ "Formula weight", "626.44" ], [ "Crystal dimensions/mm", "0.07 \u00d7 0.07 \u00d7 0.12" ], [ "Crystal system", "triclinic" ], [ "Space group", "P1\u0304" ], [ "a/\u00c5", "9.8872(5)" ], [ "b/\u00c5", "9.9387(5)" ], [ "c/\u00c5", "12.7418(6)" ], [ "\u03b1/\u00b0", "77.790(3)" ], [ "\u03b2/\u00b0", "86.260(3)" ], [ "\u03b3/\u00b0", "85.324(3)" ], [ "V/\u00c53", "1218.2(1)" ], [ "Z", "2" ], [ "F(000)", "624.00" ], [ "T/K", "183.2" ], [ "Dc/Mg m\u22123", "1.708" ], [ "\u03bc(Mo-K\u03b1)/mm\u22121", "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 > 3\u03c3(I)]", "0.041" ], [ "Goodness-of-fit", "1.18" ], [ "(\u0394\u03c1) max, min/e \u00c5\u22123", "0.92, \u22120.50" ] ] }, { "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_table": [ [ "Bond lengths/\u00c5", [ "Bond lengths/\u00c5" ], [ "1" ] ], [ "Bond lengths/\u00c5", [ "Bond lengths/\u00c5" ], [ "GS(1Br)" ] ], [ "Bond lengths/\u00c5", [ "Bond lengths/\u00c5" ], [ "2" ] ], [ "Bond lengths/\u00c5", [ "Bond lengths/\u00c5" ], [ "GS(2Br)" ] ], [ "2.014", [ "Pd\u2013E" ], [ "1" ] ], [ "2.017", [ "Pd\u2013E" ], [ "GS(1Br)" ] ], [ "2.066", [ "Pd\u2013E" ], [ "2" ] ], [ "2.093", [ "Pd\u2013E" ], [ "GS(2Br)" ] ], [ "2.00", [ "Pd\u2013C(11)" ], [ "1" ] ], [ "2.035", [ "Pd\u2013C(11)" ], [ "GS(1Br)" ] ], [ "2.020", [ "Pd\u2013C(11)" ], [ "2" ] ], [ "2.034", [ "Pd\u2013C(11)" ], [ "GS(2Br)" ] ], [ "2.5388", [ "Pd\u2013Br" ], [ "1" ] ], [ "2.558", [ "Pd\u2013Br" ], [ "GS(1Br)" ] ], [ "2.4250", [ "Pd\u2013Br" ], [ "2" ] ], [ "2.422", [ "Pd\u2013Br" ], [ "GS(2Br)" ] ], [ "1.33", [ "C(12)\u2013C(13)" ], [ "1" ] ], [ "1.366", [ "C(12)\u2013C(13)" ], [ "GS(1Br)" ] ], [ "1.328", [ "C(12)\u2013C(13)" ], [ "2" ] ], [ "1.358", [ "C(12)\u2013C(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)\u2013Pd\u2013C(21)" ], [ "1" ] ], [ "172.2", [ "C(11)\u2013Pd\u2013C(21)" ], [ "GS(1Br)" ] ], [ "173.2", [ "C(11)\u2013Pd\u2013C(21)" ], [ "2" ] ], [ "174.9", [ "C(11)\u2013Pd\u2013C(21)" ], [ "GS(2Br)" ] ], [ "85.1", [ "E\u2013Pd\u2013C(11)" ], [ "1" ] ], [ "86.1", [ "E\u2013Pd\u2013C(11)" ], [ "GS(1Br)" ] ], [ "86.7", [ "E\u2013Pd\u2013C(11)" ], [ "2" ] ], [ "87.5", [ "E\u2013Pd\u2013C(11)" ], [ "GS(2Br)" ] ], [ "179.6", [ "E\u2013Pd\u2013Br" ], [ "1" ] ], [ "180.0", [ "E\u2013Pd\u2013Br" ], [ "GS(1Br)" ] ], [ "178.9", [ "E\u2013Pd\u2013Br" ], [ "2" ] ], [ "180.0", [ "E\u2013Pd\u2013Br" ], [ "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)\u2013E\u2013Pd\u2013C(11)" ], [ "1" ] ], [ "41.3", [ "C(1)\u2013E\u2013Pd\u2013C(11)" ], [ "GS(1Br)" ] ], [ "40.6", [ "C(1)\u2013E\u2013Pd\u2013C(11)" ], [ "2" ] ], [ "41.0", [ "C(1)\u2013E\u2013Pd\u2013C(11)" ], [ "GS(2Br)" ] ], [ "49.3", [ "N(1)\u2013C(7)\u2013C(1)\u2013C(6)" ], [ "1" ] ], [ "52.7", [ "N(1)\u2013C(7)\u2013C(1)\u2013C(6)" ], [ "GS(1Br)" ] ], [ "57.2", [ "N(1)\u2013C(7)\u2013C(1)\u2013C(6)" ], [ "2" ] ], [ "56.3", [ "N(1)\u2013C(7)\u2013C(1)\u2013C(6)" ], [ "GS(2Br)" ] ], [ "95.4", [ "N(2)\u2013C(11)\u2013C(21)\u2013N(4)" ], [ "1" ] ], [ "96.8", [ "N(2)\u2013C(11)\u2013C(21)\u2013N(4)" ], [ "GS(1Br)" ] ], [ "101.3", [ "N(2)\u2013C(11)\u2013C(21)\u2013N(4)" ], [ "2" ] ], [ "91.8", [ "N(2)\u2013C(11)\u2013C(21)\u2013N(4)" ], [ "GS(2Br)" ] ] ], "tde_raw_table": [ [ "", "1", "GS(1Br)", "2", "GS(2Br)" ], [ "Bond lengths/\u00c5", "Bond lengths/\u00c5", "Bond lengths/\u00c5", "Bond lengths/\u00c5", "Bond lengths/\u00c5" ], [ "Pd\u2013E", "2.014", "2.017", "2.066", "2.093" ], [ "Pd\u2013C(11)", "2.00", "2.035", "2.020", "2.034" ], [ "Pd\u2013Br", "2.5388", "2.558", "2.4250", "2.422" ], [ "C(12)\u2013C(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)\u2013Pd\u2013C(21)", "170.9", "172.2", "173.2", "174.9" ], [ "E\u2013Pd\u2013C(11)", "85.1", "86.1", "86.7", "87.5" ], [ "E\u2013Pd\u2013Br", "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)\u2013E\u2013Pd\u2013C(11)", "42.9", "41.3", "40.6", "41.0" ], [ "N(1)\u2013C(7)\u2013C(1)\u2013C(6)", "49.3", "52.7", "57.2", "56.3" ], [ "N(2)\u2013C(11)\u2013C(21)\u2013N(4)", "95.4", "96.8", "101.3", "91.8" ] ] }, { "caption": "Table 5 Selected bond distance (\u00c5), 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_table": [ [ "2.428", [ "Pd\u2013X" ], [ "X = Cl", "GS(1Cl)" ] ], [ "2.449", [ "Pd\u2013X" ], [ "X = Cl", "TS(1Cl)" ] ], [ "2.445", [ "Pd\u2013X" ], [ "X = Cl", "Int(1Cl)" ] ], [ "2.558", [ "Pd\u2013X" ], [ "X = Br", "GS(1Br)" ] ], [ "2.595", [ "Pd\u2013X" ], [ "X = Br", "TS(1Br)" ] ], [ "2.581", [ "Pd\u2013X" ], [ "X = Br", "Int(1Br)" ] ], [ "2.742", [ "Pd\u2013X" ], [ "X = I", "GS(1I)" ] ], [ "2.783", [ "Pd\u2013X" ], [ "X = I", "TS(1I)" ] ], [ "2.774", [ "Pd\u2013X" ], [ "X = I", "Int(1I)" ] ], [ "2.015", [ "Pd\u2013C(6)" ], [ "X = Cl", "GS(1Cl)" ] ], [ "2.048", [ "Pd\u2013C(6)" ], [ "X = Cl", "TS(1Cl)" ] ], [ "2.055", [ "Pd\u2013C(6)" ], [ "X = Cl", "Int(1Cl)" ] ], [ "2.018", [ "Pd\u2013C(6)" ], [ "X = Br", "GS(1Br)" ] ], [ "2.049", [ "Pd\u2013C(6)" ], [ "X = Br", "TS(1Br)" ] ], [ "2.060", [ "Pd\u2013C(6)" ], [ "X = Br", "Int(1Br)" ] ], [ "2.020", [ "Pd\u2013C(6)" ], [ "X = I", "GS(1I)" ] ], [ "2.056", [ "Pd\u2013C(6)" ], [ "X = I", "TS(1I)" ] ], [ "2.065", [ "Pd\u2013C(6)" ], [ "X = I", "Int(1I)" ] ], [ "2.034", [ "Pd\u2013C(11)" ], [ "X = Cl", "GS(1Cl)" ] ], [ "2.016", [ "Pd\u2013C(11)" ], [ "X = Cl", "TS(1Cl)" ] ], [ "2.042", [ "Pd\u2013C(11)" ], [ "X = Cl", "Int(1Cl)" ] ], [ "2.035", [ "Pd\u2013C(11)" ], [ "X = Br", "GS(1Br)" ] ], [ "2.012", [ "Pd\u2013C(11)" ], [ "X = Br", "TS(1Br)" ] ], [ "2.037", [ "Pd\u2013C(11)" ], [ "X = Br", "Int(1Br)" ] ], [ "2.034", [ "Pd\u2013C(11)" ], [ "X = I", "GS(1I)" ] ], [ "2.015", [ "Pd\u2013C(11)" ], [ "X = I", "TS(1I)" ] ], [ "2.034", [ "Pd\u2013C(11)" ], [ "X = I", "Int(1I)" ] ], [ "2.034", [ "Pd\u2013C(21)" ], [ "X = Cl", "GS(1Cl)" ] ], [ "2.067", [ "Pd\u2013C(21)" ], [ "X = Cl", "TS(1Cl)" ] ], [ "2.042", [ "Pd\u2013C(21)" ], [ "X = Cl", "Int(1Cl)" ] ], [ "2.035", [ "Pd\u2013C(21)" ], [ "X = Br", "GS(1Br)" ] ], [ "2.067", [ "Pd\u2013C(21)" ], [ "X = Br", "TS(1Br)" ] ], [ "2.040", [ "Pd\u2013C(21)" ], [ "X = Br", "Int(1Br)" ] ], [ "2.034", [ "Pd\u2013C(21)" ], [ "X = I", "GS(1I)" ] ], [ "2.055", [ "Pd\u2013C(21)" ], [ "X = I", "TS(1I)" ] ], [ "2.034", [ "Pd\u2013C(21)" ], [ "X = I", "Int(1I)" ] ], [ "180.0", [ "C(6)\u2013Pd\u2013X" ], [ "X = Cl", "GS(1Cl)" ] ], [ "158.9", [ "C(6)\u2013Pd\u2013X" ], [ "X = Cl", "TS(1Cl)" ] ], [ "159.4", [ "C(6)\u2013Pd\u2013X" ], [ "X = Cl", "Int(1Cl)" ] ], [ "180.0", [ "C(6)\u2013Pd\u2013X" ], [ "X = Br", "GS(1Br)" ] ], [ "154.9", [ "C(6)\u2013Pd\u2013X" ], [ "X = Br", "TS(1Br)" ] ], [ "156.2", [ "C(6)\u2013Pd\u2013X" ], [ "X = Br", "Int(1Br)" ] ], [ "180.0", [ "C(6)\u2013Pd\u2013X" ], [ "X = I", "GS(1I)" ] ], [ "151.6", [ "C(6)\u2013Pd\u2013X" ], [ "X = I", "TS(1I)" ] ], [ "151.6", [ "C(6)\u2013Pd\u2013X" ], [ "X = I", "Int(1I)" ] ], [ "173.2", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Cl", "GS(1Cl)" ] ], [ "159.6", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Cl", "TS(1Cl)" ] ], [ "157.3", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Cl", "Int(1Cl)" ] ], [ "172.2", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Br", "GS(1Br)" ] ], [ "159.6", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Br", "TS(1Br)" ] ], [ "156.5", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Br", "Int(1Br)" ] ], [ "171.5", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = I", "GS(1I)" ] ], [ "158.7", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = I", "TS(1I)" ] ], [ "156.0", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = I", "Int(1I)" ] ], [ "\u221252.2", [ "C(6)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Cl", "GS(1Cl)" ] ], [ "\u221254.8", [ "C(6)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Cl", "TS(1Cl)" ] ], [ "\u221249.6", [ "C(6)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Cl", "Int(1Cl)" ] ], [ "\u221252.7", [ "C(6)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Br", "GS(1Br)" ] ], [ "\u221254.9", [ "C(6)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Br", "TS(1Br)" ] ], [ "\u221250.5", [ "C(6)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Br", "Int(1Br)" ] ], [ "\u221252.9", [ "C(6)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = I", "GS(1I)" ] ], [ "\u221255.1", [ "C(6)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = I", "TS(1I)" ] ], [ "\u221249.2", [ "C(6)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = I", "Int(1I)" ] ], [ "\u221252.2", [ "C(6)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Cl", "GS(1Cl)" ] ], [ "33.2", [ "C(6)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Cl", "TS(1Cl)" ] ], [ "49.7", [ "C(6)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Cl", "Int(1Cl)" ] ], [ "\u221252.7", [ "C(6)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Br", "GS(1Br)" ] ], [ "27.6", [ "C(6)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Br", "TS(1Br)" ] ], [ "49.1", [ "C(6)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Br", "Int(1Br)" ] ], [ "\u221252.9", [ "C(6)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = I", "GS(1I)" ] ], [ "27.2", [ "C(6)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = I", "TS(1I)" ] ], [ "49.2", [ "C(6)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = I", "Int(1I)" ] ] ], "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\u2013X", "2.428", "2.449", "2.445", "2.558", "2.595", "2.581", "2.742", "2.783", "2.774" ], [ "Pd\u2013C(6)", "2.015", "2.048", "2.055", "2.018", "2.049", "2.060", "2.020", "2.056", "2.065" ], [ "Pd\u2013C(11)", "2.034", "2.016", "2.042", "2.035", "2.012", "2.037", "2.034", "2.015", "2.034" ], [ "Pd\u2013C(21)", "2.034", "2.067", "2.042", "2.035", "2.067", "2.040", "2.034", "2.055", "2.034" ], [ "C(6)\u2013Pd\u2013X", "180.0", "158.9", "159.4", "180.0", "154.9", "156.2", "180.0", "151.6", "151.6" ], [ "C(11)\u2013Pd\u2013C(21)", "173.2", "159.6", "157.3", "172.2", "159.6", "156.5", "171.5", "158.7", "156.0" ], [ "C(6)\u2013C(1)\u2013C(7)\u2013N(1)", "\u221252.2", "\u221254.8", "\u221249.6", "\u221252.7", "\u221254.9", "\u221250.5", "\u221252.9", "\u221255.1", "\u221249.2" ], [ "C(6)\u2013C(5)\u2013C(8)\u2013N(3)", "\u221252.2", "33.2", "49.7", "\u221252.7", "27.6", "49.1", "\u221252.9", "27.2", "49.2" ] ] }, { "caption": "", "heading": 0, "tde_table": [ [ "2.294", [ "Pd\u2013X" ], [ "GS(2Cl)" ] ], [ "2.300", [ "Pd\u2013X" ], [ "TS(2Cl)" ] ], [ "2.308", [ "Pd\u2013X" ], [ "Int(2Cl)" ] ], [ "2.422", [ "Pd\u2013X" ], [ "GS(2Br)" ] ], [ "2.436", [ "Pd\u2013X" ], [ "TS(2Br)" ] ], [ "2.437", [ "Pd\u2013X" ], [ "Int(2Br)" ] ], [ "2.607", [ "Pd\u2013X" ], [ "GS(2I)" ] ], [ "2.630", [ "Pd\u2013X" ], [ "TS(2I)" ] ], [ "2.626", [ "Pd\u2013X" ], [ "Int(2I)" ] ], [ "2.081", [ "Pd\u2013N(5)" ], [ "GS(2Cl)" ] ], [ "2.159", [ "Pd\u2013N(5)" ], [ "TS(2Cl)" ] ], [ "2.174", [ "Pd\u2013N(5)" ], [ "Int(2Cl)" ] ], [ "2.093", [ "Pd\u2013N(5)" ], [ "GS(2Br)" ] ], [ "2.167", [ "Pd\u2013N(5)" ], [ "TS(2Br)" ] ], [ "2.193", [ "Pd\u2013N(5)" ], [ "Int(2Br)" ] ], [ "2.104", [ "Pd\u2013N(5)" ], [ "GS(2I)" ] ], [ "2.182", [ "Pd\u2013N(5)" ], [ "TS(2I)" ] ], [ "2.226", [ "Pd\u2013N(5)" ], [ "Int(2I)" ] ], [ "2.031", [ "Pd\u2013C(11)" ], [ "GS(2Cl)" ] ], [ "2.029", [ "Pd\u2013C(11)" ], [ "TS(2Cl)" ] ], [ "2.046", [ "Pd\u2013C(11)" ], [ "Int(2Cl)" ] ], [ "2.034", [ "Pd\u2013C(11)" ], [ "GS(2Br)" ] ], [ "2.021", [ "Pd\u2013C(11)" ], [ "TS(2Br)" ] ], [ "2.046", [ "Pd\u2013C(11)" ], [ "Int(2Br)" ] ], [ "2.037", [ "Pd\u2013C(11)" ], [ "GS(2I)" ] ], [ "2.013", [ "Pd\u2013C(11)" ], [ "TS(2I)" ] ], [ "2.035", [ "Pd\u2013C(11)" ], [ "Int(2I)" ] ], [ "2.031", [ "Pd\u2013C(21)" ], [ "GS(2Cl)" ] ], [ "2.064", [ "Pd\u2013C(21)" ], [ "TS(2Cl)" ] ], [ "2.046", [ "Pd\u2013C(21)" ], [ "Int(2Cl)" ] ], [ "2.034", [ "Pd\u2013C(21)" ], [ "GS(2Br)" ] ], [ "2.068", [ "Pd\u2013C(21)" ], [ "TS(2Br)" ] ], [ "2.037", [ "Pd\u2013C(21)" ], [ "Int(2Br)" ] ], [ "2.037", [ "Pd\u2013C(21)" ], [ "GS(2I)" ] ], [ "2.067", [ "Pd\u2013C(21)" ], [ "TS(2I)" ] ], [ "2.035", [ "Pd\u2013C(21)" ], [ "Int(2I)" ] ], [ "180.0", [ "N(5)\u2013Pd-X" ], [ "GS(2Cl)" ] ], [ "162.3", [ "N(5)\u2013Pd-X" ], [ "TS(2Cl)" ] ], [ "158.6", [ "N(5)\u2013Pd-X" ], [ "Int(2Cl)" ] ], [ "180.0", [ "N(5)\u2013Pd-X" ], [ "GS(2Br)" ] ], [ "158.8", [ "N(5)\u2013Pd-X" ], [ "TS(2Br)" ] ], [ "155.1", [ "N(5)\u2013Pd-X" ], [ "Int(2Br)" ] ], [ "180.0", [ "N(5)\u2013Pd-X" ], [ "GS(2I)" ] ], [ "153.5", [ "N(5)\u2013Pd-X" ], [ "TS(2I)" ] ], [ "147.9", [ "N(5)\u2013Pd-X" ], [ "Int(2I)" ] ], [ "175.8", [ "C(11)\u2013Pd\u2013C(21)" ], [ "GS(2Cl)" ] ], [ "163.6", [ "C(11)\u2013Pd\u2013C(21)" ], [ "TS(2Cl)" ] ], [ "161.0", [ "C(11)\u2013Pd\u2013C(21)" ], [ "Int(2Cl)" ] ], [ "174.9", [ "C(11)\u2013Pd\u2013C(21)" ], [ "GS(2Br)" ] ], [ "163.8", [ "C(11)\u2013Pd\u2013C(21)" ], [ "TS(2Br)" ] ], [ "161.1", [ "C(11)\u2013Pd\u2013C(21)" ], [ "Int(2Br)" ] ], [ "173.8", [ "C(11)\u2013Pd\u2013C(21)" ], [ "GS(2I)" ] ], [ "164.1", [ "C(11)\u2013Pd\u2013C(21)" ], [ "TS(2I)" ] ], [ "160.8", [ "C(11)\u2013Pd\u2013C(21)" ], [ "Int(2I)" ] ], [ "\u221255.9", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "GS(2Cl)" ] ], [ "\u221266.5", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "TS(2Cl)" ] ], [ "\u221261.3", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "Int(2Cl)" ] ], [ "\u221256.4", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "GS(2Br)" ] ], [ "\u221267.2", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "TS(2Br)" ] ], [ "\u221261.2", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "Int(2Br)" ] ], [ "\u221256.9", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "GS(2I)" ] ], [ "\u221266.4", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "TS(2I)" ] ], [ "\u221260.9", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "Int(2I)" ] ], [ "\u221255.9", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "GS(2Cl)" ] ], [ "50.9", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "TS(2Cl)" ] ], [ "61.3", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "Int(2Cl)" ] ], [ "\u221256.4", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "GS(2Br)" ] ], [ "43.6", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "TS(2Br)" ] ], [ "61.7", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "Int(2Br)" ] ], [ "\u221256.9", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "GS(2I)" ] ], [ "33.2", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "TS(2I)" ] ], [ "60.9", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "Int(2I)" ] ] ], "tde_raw_table": [ [ "", "GS(2Cl)", "TS(2Cl)", "Int(2Cl)", "GS(2Br)", "TS(2Br)", "Int(2Br)", "GS(2I)", "TS(2I)", "Int(2I)" ], [ "Pd\u2013X", "2.294", "2.300", "2.308", "2.422", "2.436", "2.437", "2.607", "2.630", "2.626" ], [ "Pd\u2013N(5)", "2.081", "2.159", "2.174", "2.093", "2.167", "2.193", "2.104", "2.182", "2.226" ], [ "Pd\u2013C(11)", "2.031", "2.029", "2.046", "2.034", "2.021", "2.046", "2.037", "2.013", "2.035" ], [ "Pd\u2013C(21)", "2.031", "2.064", "2.046", "2.034", "2.068", "2.037", "2.037", "2.067", "2.035" ], [ "N(5)\u2013Pd-X", "180.0", "162.3", "158.6", "180.0", "158.8", "155.1", "180.0", "153.5", "147.9" ], [ "C(11)\u2013Pd\u2013C(21)", "175.8", "163.6", "161.0", "174.9", "163.8", "161.1", "173.8", "164.1", "160.8" ], [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)", "\u221255.9", "\u221266.5", "\u221261.3", "\u221256.4", "\u221267.2", "\u221261.2", "\u221256.9", "\u221266.4", "\u221260.9" ], [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)", "\u221255.9", "50.9", "61.3", "\u221256.4", "43.6", "61.7", "\u221256.9", "33.2", "60.9" ] ] }, { "caption": "Table 6 Activation energy and relative energy (kJ mol\u22121) 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 \u0394E\u2020 and \u0394E. 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_table": [ [ "69.9", [ "X = Cl" ], [ "[{CCC}PdX]", "\u0394E\u2020", "GP" ] ], [ "69.5", [ "X = Cl" ], [ "[{CCC}PdX]", "\u0394E\u2020", "PCM" ] ], [ "68.0", [ "X = Cl" ], [ "[{CCC}PdX]", "\u0394E", "GP" ] ], [ "68.9", [ "X = Cl" ], [ "[{CCC}PdX]", "\u0394E", "PCM" ] ], [ "73.2", [ "X = Cl" ], [ "[{CNC}PdX]+", "\u0394E\u2020", "GP" ] ], [ "75.5", [ "X = Cl" ], [ "[{CNC}PdX]+", "\u0394E\u2020", "PCM" ] ], [ "74.9", [ "X = Cl" ], [ "[{CNC}PdX]+", "\u0394E", "GP" ] ], [ "71.8", [ "X = Cl" ], [ "[{CNC}PdX]+", "\u0394E", "PCM" ] ], [ "71.4", [ "X = Br" ], [ "[{CCC}PdX]", "\u0394E\u2020", "GP" ] ], [ "72.3", [ "X = Br" ], [ "[{CCC}PdX]", "\u0394E\u2020", "PCM" ] ], [ "68.2", [ "X = Br" ], [ "[{CCC}PdX]", "\u0394E", "GP" ] ], [ "71.2", [ "X = Br" ], [ "[{CCC}PdX]", "\u0394E", "PCM" ] ], [ "73.0", [ "X = Br" ], [ "[{CNC}PdX]+", "\u0394E\u2020", "GP" ] ], [ "75.3", [ "X = Br" ], [ "[{CNC}PdX]+", "\u0394E\u2020", "PCM" ] ], [ "72.3", [ "X = Br" ], [ "[{CNC}PdX]+", "\u0394E", "GP" ] ], [ "66.6", [ "X = Br" ], [ "[{CNC}PdX]+", "\u0394E", "PCM" ] ], [ "72.5", [ "X = I" ], [ "[{CCC}PdX]", "\u0394E\u2020", "GP" ] ], [ "72.4", [ "X = I" ], [ "[{CCC}PdX]", "\u0394E\u2020", "PCM" ] ], [ "69.0", [ "X = I" ], [ "[{CCC}PdX]", "\u0394E", "GP" ] ], [ "66.5", [ "X = I" ], [ "[{CCC}PdX]", "\u0394E", "PCM" ] ], [ "72.9", [ "X = I" ], [ "[{CNC}PdX]+", "\u0394E\u2020", "GP" ] ], [ "79.3", [ "X = I" ], [ "[{CNC}PdX]+", "\u0394E\u2020", "PCM" ] ], [ "69.7", [ "X = I" ], [ "[{CNC}PdX]+", "\u0394E", "GP" ] ], [ "67.2", [ "X = I" ], [ "[{CNC}PdX]+", "\u0394E", "PCM" ] ] ], "tde_raw_table": [ [ "", "[{CCC}PdX]", "[{CCC}PdX]", "[{CCC}PdX]", "[{CCC}PdX]", "[{CNC}PdX]+", "[{CNC}PdX]+", "[{CNC}PdX]+", "[{CNC}PdX]+" ], [ "", "\u0394E\u2020", "\u0394E\u2020", "\u0394E", "\u0394E", "\u0394E\u2020", "\u0394E\u2020", "\u0394E", "\u0394E" ], [ "", "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" ] ] }, { "caption": "Table 7 Selected bond distance (\u00c5), 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_table": [ [ "2.390", [ "Pd\u2013X" ], [ "X = Cl", "GS(2Cl2)" ] ], [ "2.367", [ "Pd\u2013X" ], [ "X = Cl", "TS(2Cl2)" ] ], [ "2.370", [ "Pd\u2013X" ], [ "X = Cl", "Int(2Cl2)" ] ], [ "2.531", [ "Pd\u2013X" ], [ "X = Br", "GS(2Br2)" ] ], [ "2.503", [ "Pd\u2013X" ], [ "X = Br", "TS(2Br2)" ] ], [ "2.505", [ "Pd\u2013X" ], [ "X = Br", "Int(2Br2)" ] ], [ "2.730", [ "Pd\u2013X" ], [ "X = I", "GS(2I2)" ] ], [ "2.695", [ "Pd\u2013X" ], [ "X = I", "TS(2I2)" ] ], [ "2.695", [ "Pd\u2013X" ], [ "X = I", "Int(2I2)" ] ], [ "2.578", [ "Pd\u2013N(5)" ], [ "X = Cl", "GS(2Cl2)" ] ], [ "2.657", [ "Pd\u2013N(5)" ], [ "X = Cl", "TS(2Cl2)" ] ], [ "2.753", [ "Pd\u2013N(5)" ], [ "X = Cl", "Int(2Cl2)" ] ], [ "2.554", [ "Pd\u2013N(5)" ], [ "X = Br", "GS(2Br2)" ] ], [ "2.635", [ "Pd\u2013N(5)" ], [ "X = Br", "TS(2Br2)" ] ], [ "2.735", [ "Pd\u2013N(5)" ], [ "X = Br", "Int(2Br2)" ] ], [ "2.525", [ "Pd\u2013N(5)" ], [ "X = I", "GS(2I2)" ] ], [ "2.605", [ "Pd\u2013N(5)" ], [ "X = I", "TS(2I2)" ] ], [ "2.713", [ "Pd\u2013N(5)" ], [ "X = I", "Int(2I2)" ] ], [ "2.015", [ "Pd\u2013C(11)" ], [ "X = Cl", "GS(2Cl2)" ] ], [ "2.016", [ "Pd\u2013C(11)" ], [ "X = Cl", "TS(2Cl2)" ] ], [ "2.023", [ "Pd\u2013C(11)" ], [ "X = Cl", "Int(2Cl2)" ] ], [ "2.015", [ "Pd\u2013C(11)" ], [ "X = Br", "GS(2Br2)" ] ], [ "2.015", [ "Pd\u2013C(11)" ], [ "X = Br", "TS(2Br2)" ] ], [ "2.021", [ "Pd\u2013C(11)" ], [ "X = Br", "Int(2Br2)" ] ], [ "2.017", [ "Pd\u2013C(11)" ], [ "X = I", "GS(2I2)" ] ], [ "2.016", [ "Pd\u2013C(11)" ], [ "X = I", "TS(2I2)" ] ], [ "2.022", [ "Pd\u2013C(11)" ], [ "X = I", "Int(2I2)" ] ], [ "2.023", [ "Pd\u2013C(21)" ], [ "X = Cl", "GS(2Cl2)" ] ], [ "2.021", [ "Pd\u2013C(21)" ], [ "X = Cl", "TS(2Cl2)" ] ], [ "2.022", [ "Pd\u2013C(21)" ], [ "X = Cl", "Int(2Cl2)" ] ], [ "2.020", [ "Pd\u2013C(21)" ], [ "X = Br", "GS(2Br2)" ] ], [ "2.020", [ "Pd\u2013C(21)" ], [ "X = Br", "TS(2Br2)" ] ], [ "2.021", [ "Pd\u2013C(21)" ], [ "X = Br", "Int(2Br2)" ] ], [ "2.018", [ "Pd\u2013C(21)" ], [ "X = I", "GS(2I2)" ] ], [ "2.018", [ "Pd\u2013C(21)" ], [ "X = I", "TS(2I2)" ] ], [ "2.022", [ "Pd\u2013C(21)" ], [ "X = I", "Int(2I2)" ] ], [ "94.4", [ "N(5)\u2013Pd\u2013X" ], [ "X = Cl", "GS(2Cl2)" ] ], [ "93.9", [ "N(5)\u2013Pd\u2013X" ], [ "X = Cl", "TS(2Cl2)" ] ], [ "99.0", [ "N(5)\u2013Pd\u2013X" ], [ "X = Cl", "Int(2Cl2)" ] ], [ "96.3", [ "N(5)\u2013Pd\u2013X" ], [ "X = Br", "GS(2Br2)" ] ], [ "94.2", [ "N(5)\u2013Pd\u2013X" ], [ "X = Br", "TS(2Br2)" ] ], [ "99.3", [ "N(5)\u2013Pd\u2013X" ], [ "X = Br", "Int(2Br2)" ] ], [ "98.7", [ "N(5)\u2013Pd\u2013X" ], [ "X = I", "GS(2I2)" ] ], [ "94.9", [ "N(5)\u2013Pd\u2013X" ], [ "X = I", "TS(2I2)" ] ], [ "100.2", [ "N(5)\u2013Pd\u2013X" ], [ "X = I", "Int(2I2)" ] ], [ "85.4", [ "N(5)\u2013Pd\u2013C(11)" ], [ "X = Cl", "GS(2Cl2)" ] ], [ "90.7", [ "N(5)\u2013Pd\u2013C(11)" ], [ "X = Cl", "TS(2Cl2)" ] ], [ "88.1", [ "N(5)\u2013Pd\u2013C(11)" ], [ "X = Cl", "Int(2Cl2)" ] ], [ "85.3", [ "N(5)\u2013Pd\u2013C(11)" ], [ "X = Br", "GS(2Br2)" ] ], [ "90.5", [ "N(5)\u2013Pd\u2013C(11)" ], [ "X = Br", "TS(2Br2)" ] ], [ "88.3", [ "N(5)\u2013Pd\u2013C(11)" ], [ "X = Br", "Int(2Br2)" ] ], [ "86.0", [ "N(5)\u2013Pd\u2013C(11)" ], [ "X = I", "GS(2I2)" ] ], [ "90.5", [ "N(5)\u2013Pd\u2013C(11)" ], [ "X = I", "TS(2I2)" ] ], [ "88.5", [ "N(5)\u2013Pd\u2013C(11)" ], [ "X = I", "Int(2I2)" ] ], [ "168.6", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Cl", "GS(2Cl2)" ] ], [ "172.0", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Cl", "TS(2Cl2)" ] ], [ "175.4", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Cl", "Int(2Cl2)" ] ], [ "169.9", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Br", "GS(2Br2)" ] ], [ "172.3", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Br", "TS(2Br2)" ] ], [ "176.1", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = Br", "Int(2Br2)" ] ], [ "171.9", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = I", "GS(2I2)" ] ], [ "173.2", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = I", "TS(2I2)" ] ], [ "176.5", [ "C(11)\u2013Pd\u2013C(21)" ], [ "X = I", "Int(2I2)" ] ], [ "\u221263.1", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Cl", "GS(2Cl2)" ] ], [ "\u221294.4", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Cl", "TS(2Cl2)" ] ], [ "\u221293.1", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Cl", "Int(2Cl2)" ] ], [ "\u221256.9", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Br", "GS(2Br2)" ] ], [ "\u221291.3", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Br", "TS(2Br2)" ] ], [ "\u221292.3", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = Br", "Int(2Br2)" ] ], [ "\u221253.2", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = I", "GS(2I2)" ] ], [ "\u221287.4", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = I", "TS(2I2)" ] ], [ "\u221290.7", [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)" ], [ "X = I", "Int(2I2)" ] ], [ "\u221247.0", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Cl", "GS(2Cl2)" ] ], [ "31.1", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Cl", "TS(2Cl2)" ] ], [ "93.2", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Cl", "Int(2Cl2)" ] ], [ "\u221251.6", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Br", "GS(2Br2)" ] ], [ "24.8", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Br", "TS(2Br2)" ] ], [ "92.3", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = Br", "Int(2Br2)" ] ], [ "\u221253.0", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = I", "GS(2I2)" ] ], [ "19.2", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = I", "TS(2I2)" ] ], [ "90.7", [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)" ], [ "X = I", "Int(2I2)" ] ] ], "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\u2013X", "2.390", "2.367", "2.370", "2.531", "2.503", "2.505", "2.730", "2.695", "2.695" ], [ "Pd\u2013N(5)", "2.578", "2.657", "2.753", "2.554", "2.635", "2.735", "2.525", "2.605", "2.713" ], [ "Pd\u2013C(11)", "2.015", "2.016", "2.023", "2.015", "2.015", "2.021", "2.017", "2.016", "2.022" ], [ "Pd\u2013C(21)", "2.023", "2.021", "2.022", "2.020", "2.020", "2.021", "2.018", "2.018", "2.022" ], [ "N(5)\u2013Pd\u2013X", "94.4", "93.9", "99.0", "96.3", "94.2", "99.3", "98.7", "94.9", "100.2" ], [ "N(5)\u2013Pd\u2013C(11)", "85.4", "90.7", "88.1", "85.3", "90.5", "88.3", "86.0", "90.5", "88.5" ], [ "C(11)\u2013Pd\u2013C(21)", "168.6", "172.0", "175.4", "169.9", "172.3", "176.1", "171.9", "173.2", "176.5" ], [ "N(5)\u2013C(1)\u2013C(7)\u2013N(1)", "\u221263.1", "\u221294.4", "\u221293.1", "\u221256.9", "\u221291.3", "\u221292.3", "\u221253.2", "\u221287.4", "\u221290.7" ], [ "N(5)\u2013C(5)\u2013C(8)\u2013N(3)", "\u221247.0", "31.1", "93.2", "\u221251.6", "24.8", "92.3", "\u221253.0", "19.2", "90.7" ] ] }, { "caption": "Table 8 Activation energy and relative energy (kJ mol\u22121) of the intermediate for the two-step fluxional process [{CNC}PdX2]\n(X = Cl, Br, I). See Scheme 1 for definition of \u0394E\u2020 and \u0394E. 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_table": [ [ "11.2", [ "X = Cl" ], [ "\u0394E\u2020", "GP" ] ], [ "10.4", [ "X = Cl" ], [ "\u0394E\u2020", "PCM" ] ], [ "0.2", [ "X = Cl" ], [ "\u0394E", "GP" ] ], [ "0.8", [ "X = Cl" ], [ "\u0394E", "PCM" ] ], [ "10.3", [ "X = Br" ], [ "\u0394E\u2020", "GP" ] ], [ "11.9", [ "X = Br" ], [ "\u0394E\u2020", "PCM" ] ], [ "\u22124.1", [ "X = Br" ], [ "\u0394E", "GP" ] ], [ "\u22121.4", [ "X = Br" ], [ "\u0394E", "PCM" ] ], [ "10.1", [ "X = I" ], [ "\u0394E\u2020", "GP" ] ], [ "12.8", [ "X = I" ], [ "\u0394E\u2020", "PCM" ] ], [ "\u22128.0", [ "X = I" ], [ "\u0394E", "GP" ] ], [ "\u22123.0", [ "X = I" ], [ "\u0394E", "PCM" ] ] ], "tde_raw_table": [ [ "", "\u0394E\u2020", "\u0394E\u2020", "\u0394E", "\u0394E" ], [ "", "GP", "PCM", "GP", "PCM" ], [ "X = Cl", "11.2", "10.4", "0.2", "0.8" ], [ "X = Br", "10.3", "11.9", "\u22124.1", "\u22121.4" ], [ "X = I", "10.1", "12.8", "\u22128.0", "\u22123.0" ] ] } ], "figures": [ { "links": [ "http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-f1.gif" ], "caption": "X-Ray structure of the pyridine complex." }, { "links": [ "http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-f2.gif" ], "caption": "Optimized geometry for Pd{CCC}Br, GS(1Br), and Pd{CNC}Br+, GS(2Br), at the B3PW91 level." }, { "links": [ "http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-f3.gif" ], "caption": "Mechanism for interconversion for Pd{CCC}Br. Energies are in kJ mol\u22121." }, { "links": [ "http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-s1.gif" ], "caption": "" }, { "links": [ "http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-f4.gif" ], "caption": "Mechanism for interconversion for Pd{CNC}2+. Energies are in kJ mol\u22121." }, { "links": [ "http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2003/DT/b210784h/b210784h-f5.gif" ], "caption": "Mechanism for interconversion for [Pd{CNC}(Br)2]. Energies are in kJ mol\u22121." } ], "records": [ { "Crystal": { "density": { "Density": { "units": "(10^6.0) * Gram^(1.0) Meter^(-3.0)", "value": [ 1.708 ], "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "raw_units": "Mgm\u22123", "raw_value": "1.708", "specifier": "Dc" } }, "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ], "smiles": [] }, "elements": [ "N", "F", "Pd", "C", "H", "B" ] }, "specifier": "system", "cde2_method": "AutoTableParser", "cell_params": { "UnitCell": { "system": "triclinic", "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "specifier": "Crystal system", "cell_volume": { "CellVolume": { "error": 0.1, "units": "Angstrom^(3.0)", "value": [ 1218.2 ], "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "raw_units": "\u00c53", "raw_value": "1218.2(1)", "specifier": "V" } }, "space_group": { "SpaceGroup": { "symbol": "P1\u0304", "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "specifier": "Space group" } 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"CellAngleAlpha": { "error": 0.003, "units": "Degrees^(1.0)", "value": [ 77.79 ], "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "raw_units": "\u00b0", "raw_value": "77.790(3)", "specifier": "\u03b1" } }, "lattice_param_gamma": { "CellAngleGamma": { "error": 0.003, "units": "Degrees^(1.0)", "value": [ 85.324 ], "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "raw_units": "\u00b0", "raw_value": "85.324(3)", "specifier": "\u03b3" } } } }, "cde2_updated": false, "diffraction_params": { "DiffractionParams": { "z": { "Z": { "value": [ 2.0 ], "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "raw_value": "2", "specifier": "Z" } }, "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "specifier": "Crystal system", "structure_factor": { "F": { "value": [ 624.0 ], "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "raw_value": "624.00", "specifier": "F(000)" } }, "applied_temperature": { "AppliedTemperature": { "units": "Kelvin^(1.0)", "value": [ 183.2 ], "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "raw_units": "K", "raw_value": "183.2", "specifier": "T" } }, "absorption_coefficient": { "AbsorptionCoefficient": { "units": "(10^3.0) * Meter^(-1.0)", "value": [ 0.845 ], "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "raw_units": "mm\u22121", "raw_value": "0.845", "specifier": "\u03bc(Mo-K\u03b1)" } } } }, "formula_weight_no_dim": { "FormulaWeightNoDim": { "value": [ 626.44 ], "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "raw_value": "626.44", "specifier": "Formula weight" } } } }, { "Crystal": { "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ], "smiles": [] }, "elements": [ "N", "F", "Pd", "C", "H", "B" ] }, "specifier": "Space group", "cde2_method": "AutoTableParser", "cell_params": { "UnitCell": { "system": "triclinic", "compound": { "Compound": { "names": [ "C20H22B2F8N6Pd" ] } }, "specifier": "Crystal system", "cell_volume": { 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Miecznikowski", "Stephan Gr\u00fcndemann", "Martin Albrecht", "Claire M\u00e9gret", "Eric Clot", "Jack W. Faller", "Odile Eisenstein", "Robert H. Crabtree", "John R. Miecznikowski", "Stephan Gr\u00fcndemann", "Martin Albrecht", "Claire M\u00e9gret", "Eric Clot", "Jack W. Faller", "Odile Eisenstein", "Robert H. Crabtree" ], "journal": "Dalton Transactions", "pdf_url": "http://pubs.rsc.org/en/Content/ArticlePDF/2003/DT/B210784H", "html_url": "http://pubs.rsc.org/en/Content/ArticleLanding/2003/DT/B210784H", "lastpage": "838", "copyright": "", "firstpage": "831", "publisher": "Royal Society of Chemistry", "definitions": [ { "end": 12, "start": 7, "tokens": [ [ "CCC", "NN" ], [ "=", "JJ" ], [ "(", "-LRB-" ], [ "\u03b73-C,C\u2032,C\u2033", "NN" ], [ ")", "-RRB-" ] ], "specifier": "\u03b73-C,C\u2032,C\u2033", "definition": "CCC =" }, { "end": 23, "start": 20, "tokens": [ [ "=", "JJ" ], [ "(\u03b73-C,C\u2032,N)(2,6-bis{[N-methyl-N\u2032-methylene]imidazol-2-ylidene}pyridine)", "B-CM" ], [ ")", "-RRB-" ] ], "specifier": "(\u03b73-C,C\u2032,N)(2,6-bis{[N-methyl-N\u2032-methylene]imidazol-2-ylidene}pyridine)", "definition": "=" }, { "end": 22, "start": 19, "tokens": [ [ "pincer", "NN" ], [ "(", "-LRB-" ], [ "Table", "NN" ] ], "specifier": "Table", "definition": "pincer" }, { "end": 32, "start": 28, 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