3.2.2. Synthesis of [Pd(PP)(PR3)Cl][BArF24] Compounds
Approximately 100 mg of the appropriate [Pd2(PP)2(μ-Cl)2][BArF24]2 complex was placed in a flask equipped with a stir bar. For air-stable phosphines, two molar equivalents of the desired phosphine were added to the flask, which was then degassed and filled with argon before the CH2Cl2 (10 mL) was added. For air-sensitive phosphines, the flask was degassed, filled with argon, and then CH2Cl2 (10 mL), followed by two molar equivalents of the appropriate phosphine, were added. The reaction was then stirred overnight. The volume of the solution was reduced to approximately 3 mL and then layered with Et2O and placed in a −10 °C freezer for 48 h. The resulting solid was collected by filtration, washed with Et2O, and dried under vacuum.
[Pd(dippf)(PMe3)Cl][BArF24]
The product was isolated as an orange solid in 70% yield. 1H NMR (CD2Cl2) δ: 7.64 (br s, 8H, BArF24), 7.48 (br s, 4H, BArF24), 4.50 (m, 8H, -C5H4), 2.96 (m, 2H, -CHMe2), 2.30 (m, 2H, -CHMe2), 1.65 (d, 2JP-H = 10.4 Hz, 9H, -Me), 1.12 (m, 18H, -CHMe2). 13C{1H} NMR (CD2Cl2): δ 161.7 (q, 1JB-C = 49.9 Hz, no DEPT, BArF24), 134.8 (m, DEPT +, BArF24), 128.8 (m, no DEPT, BArF24), 124.6 (q, 1JF-C = 272.3 Hz, no DEPT, BArF24), 117.5 (m, DEPT +, BArF24), 74.5 (d, 2JP-C = 7.5 Hz, DEPT +, -C5H4), 74.0 (d, 2JP-C = 6.6 Hz, DEPT +, -C5H4), 73.4 (d, 3JP-C = 5.2 Hz, DEPT +, -C5H4), 73.3 (d, 3JP-C = 6.4 Hz, DEPT +, -C5H4), 72.4 (m, no DEPT, -C5H4), 28.0 (d, 1JP-C = 26.2 Hz, -CHMe2), 19.6 (s, DEPT +, -CHMe2), 17.1 (d, 1JP-C = 30.2 Hz, DEPT +, -PCH3). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 67.7 (dd, 2JP-P = 31.2 and 12.0 Hz, -PiPr2), 57.9 (dd, 2JP-P = 446.1 and 12.0, -PiPr2), −11.0 (dd, 2JP-P = 446.1 and 31.2 Hz, -PMe3). Anal. Calc. for C47H57BClF24FeP3Pd: C, 44.34; H, 4.51. Found: C, 44.22; H, 4.44%.
[Pd(dippf)(PPh3)Cl][BArF24]
The product was isolated as an orange solid in 58% yield. 1H NMR (CD2Cl2) δ: 7.64 (br s, 11H, -Ph and BArF24), 7.54–7.38 (m, 13H, -Ph and BArF24), 7.23 (m, 3H, -Ph), 4.57 (AA′XX′, 2H, -C5H4), 4.52 (AA′XX′, 2H, -C5H4), 4.50 (AA′XX′, 2H, -C5H4), 4.48 (AA′XX′, 2H, -C5H4), 2.97 (m, 2H, -CHMe2), 2.49 (m, 2H, -CHMe2), 1.18 (m, 18H, -CHMe2). 13C{1H} NMR (CD2Cl2): δ 161.9 (q, 1JB-C = 49.8 Hz, no DEPT, BArF24), 135.4 (d, 3JP-C = 10.1 Hz, DEPT +m -Ph), 134.9 (m, DEPT +, BArF24), 131.9 (d, 4JP-C = 3.0 Hz, DEPT +, -Ph), 131.0 (d, 1JP-C = 47.6 Hz, no DEPT, -Ph), 129.1 (m, no DEPT, BArF24), 128.9 (d, 2JP-C = 10.4 Hz, DEPT +, -Ph), 124.7 (q, 1JF-C = 272.5 Hz, no DEPT, BArF24), 117.6 (m, DEPT +, BArF24), 74.7 (d, 2JP-C = 7.4 Hz, DEPT +, -C5H4), 74.2 (d, 2JP-C = 6.7 Hz, DEPT +, -C5H4), 73.6 (d, 3JP-C = 5.6 Hz, DEPT +, -C5H4), 73.3 (d, 3JP-C = 6.6 Hz, DEPT +, -C5H4), 72.6 (m, no DEPT, -C5H4), 28.2 (d, 1JP-C = 26.5 Hz, DEPT +, -CHMe2), 19.8 (s, DEPT +, -CHMe2). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 65.5 (dd, 2JP-P = 24.0 and 14.1 Hz, -PiPr2), 62.5 (dd, 2JP-P = 428.1 and 14.1, -PiPr2), 23.7 (dd, 2JP-P = 428.1 and 24.0 Hz, -PPh3). Anal. Calc. for C72H63BClF24FeP3Pd: C, 54.76; H, 4.02. Found: C, 54.87; H, 4.29%.
[Pd(dippf)(PPh2Fc)Cl][BArF24]
The product was isolated as a red–purple solid in 59% yield. 1H NMR (CD2Cl2) δ: 7.83 (br s, 4H, -Ph), 7.65 (br s, 8H, BArF24), 7.46 (m, 6H, -Ph and BArF24), 7.27 (m, 4H, -Ph), 4.57 (AA′XX′, 2H, -C5H4), 4.52 (AA′XX′, 2H, -C5H4), 4.48 (AA′XX′, 2H, -C5H4), 4.45 (AA′XX′, 2H, -C5H4), 4.41 (AA′XX′, 2H, -C5H4), 3.97 (AA′XX′, 2H, -C5H4), 3.94 (s, 5H, Cp), 2.93 (m, 4H, -CHMe2), 1.18 (m, 18H, -CHMe2). 13C{1H} NMR (CD2Cl2): δ 161.9 (q, 1JB-C = 49.9 Hz, no DEPT, BArF24), 134.9 (m, DEPT +, BArF24), 134.8 (d, 1JP-C = 47.5 Hz, no DEPT, -Ph), 133.5 (d, 2JP-C = 19.3 Hz, DEPT +, -Ph), 131.8 (d, 4JP-C = 2.6 Hz, DEPT +, -Ph), 129.0 (m, no DEPT, BArF24), 128.3 (d, 3JP-C = 10.6 Hz, DEPT +, -Ph), 124.7 (q, 1JF-C = 272.5 Hz, no DEPT, BArF24), 117.6 (m, DEPT +, BArF24), 74.6 (d, 3JP-C = 7.1 Hz, DEPT +, -C5H4), 74.3 (d, 1JP-C = 24.5 Hz, no DEPT, -C5H4), 74.2 (d, 3JP-C = 6.8 Hz, DEPT +, -C5H4), 74.1 (d, 1JP-C = 34.9 Hz, no DEPT, -C5H4), 73.5 (d, 3JP-C = 5.5 Hz, DEPT +, -C5H4), 73.3 (d, 2JP-C = 9.8 Hz, DEPT +, -C5H4), 73.1 (d, 2JP-C = 6.2 Hz, DEPT +, -C5H4), 72.9 (d, 1JP-C = 13.4 Hz, no DEPT, -C5H4), 71.7 (d, 2JP-C = 8.4 Hz, DEPT +, -C5H4), 71.4 (s, DEPT +, Cp), 28.0 (d, 1JP-C = 26.5 Hz, DEPT +, -CHMe2), 19.8 (s, DEPT +, -CHMe2). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 64.1 (dd, 2JP-P = 23.5 and 9.7 Hz, -PiPr2), 58.8 (dd, 2JP-P = 434.6 and 9.7, -PiPr2), 20.0 (dd, 2JP-P = 434.6 and 23.5 Hz, -PPh2Fc). Anal. Calc. for C76H67BClF24Fe2P3Pd: C, 54.10; H, 4.00. Found: C, 54.25; H, 4.11%.
[Pd(dppdtbpf)(PMe3)Cl][BArF24]
The product was isolated as a red solid in 73% yield. 1H NMR (CD2Cl2) δ: 7.96 (m, 4H, -Ph), 7.64 (br s, 8H, BArF24), 7.55 (m, 6H, -Ph), 7.48 (br s, 4H, BArF24), 4.69 (AA′XX′, 2H, -C5H4), 4.44 (AA′XX′, 2H, -C5H4), 4.29 (AA′XX′, 2H, -C5H4), 4.16 (AA′XX′, 2H, -C5H4), 1.57 (s, 18H, -CMe3), 1.65 (d, 2JP-H = 14.5 Hz, 9H, -PMe3). 13C{1H} NMR (CD2Cl2): δ 161.7 (q, 1JB-C = 49.8 Hz, no DEPT, BArF24), 134.8 (m, DEPT +, BArF24), 134.1 (d, 2JP-C = 13.6 Hz, DEPT +, -Ph), 138.4 (s, DEPT +, -Ph), 132.3 (d, 1JP-C = 50.7 Hz, no DEPT, -Ph), 129.7 (d, 3JP-C = 11.6 Hz, DEPT +, -Ph), 128.9 (m, no DEPT, BArF24), 124.6 (q, 1JF-C = 272.4 Hz, no DEPT, BArF24), 117.5 (m, DEPT +, BArF24), 77.3 (d, 2JP-C = 11.0 Hz, DEPT +, -C5H4), 76.5 (d, 1JP-C = 61.5 Hz, no DEPT, -C5H4), 75.3 (d, 3JP-C = 6.7 Hz, DEPT +, -C5H4), 73.2 (m, DEPT +, -C5H4), 41.0 (d, 1JP-C = 14.3 Hz, no DEPT, -CMe3), 31.6 (s, DEPT +, -CMe3), 14.8 (d, 1JP-C = 33.2 Hz, DEPT +, -PCH3). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 74.0 (dd, 2JP-P = 430.7 and 5.5 Hz, -PtBu2), 43.5 (dd, 2JP-P = 23.5 and 5.5 Hz, -PPh2), −8.0 (dd, 2JP-P = 430.7 and 23.5 Hz, -PMe3). Anal. Calc. for C65H57BClF24FeP3Pd: C, 52.42; H, 3.86. Found: C, 52.03; H, 3.75%.
[Pd(dppdtbpf)(PPh3)Cl][BArF24]
The product was isolated as a red solid in 98% yield. 1H NMR (CD2Cl2) δ: 8.00–7.05 (m, 37H, -Ph and BArF24), 7.48 (m, 8H, BArF24), 4.94 (AA′XX′, 2H, -C5H4), 4.59 (AA′XX′, 2H, -C5H4), 4.33 (AA′XX′, 2H, -C5H4), 3.63 (AA′XX′, 2H, -C5H4), 1.75 (d, 3JP-H = 14.7 Hz, 18H, -Me). 13C{1H} NMR (CD2Cl2): δ 161.7 (q, 1JB-C = 49.9 Hz, no DEPT, BArF24), 135.1 (d, 3JP-C = 9.4 Hz, DEPT +, -Ph), 134.8 (m, DEPT +, BArF24), 133.6 (d, 3JP-C = 9.0 Hz, DEPT +, -Ph), 132.5 (d, 4JP-C = 2.8 Hz, DEPT +, -Ph), 130.8 (d, 4JP-C = 2.9 Hz, DEPT +, -Ph), 129.9 (m, no DEPT, -Ph), 129.2 (d, 2JP-C = 11.6 Hz, DEPT +, -Ph), 129.0 (m, no DEPT, -Ph), 128.6 (m, no DEPT, BArF24), 128.2 (d, 2JP-C = 10.4 Hz, DEPT +, -Ph), 124.6 (q, 1JF-C = 272.3 Hz, no DEPT, BArF24), 117.5 (m, DEPT +, BArF24), 77.3 (m, DEPT +, -C5H4), 75.7 (m, no DEPT, -C5H4), 73.3 (m, DEPT +, -C5H4), 42.5 (d, 1JP-C = 15.4 Hz, no DEPT, -CMe3), 32.0 (s, DEPT +, -Me). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 78.8 (dd, 2JP-P = 423.0 and 6.2 Hz, -PtBu2), 44.1 (dd, 2JP-P = 19.6 and 6.2, -PPh2), 24.2 (dd, 2JP-P = 423.0 and 19.6 Hz, -PPh3). Anal. Calc. for C80H63BClF24FeP3Pd: C, 57.35; H, 3.74. Found: C, 57.12; H, 3.84%.
[Pd(dppdtbpf)(PPh2Fc)Cl][BArF24]
The product was isolated as a red–purple solid in 66% yield. 1H NMR (CD2Cl2) δ: 7.90–6.90 (m, 24H, -Ph and BArF24), 5.25 (AA′XX′, 2H, -C5H4), 4.74 (AA′XX′, 2H, -C5H4), 4.42 (AA′XX′, 2H, -C5H4), 4.38 (AA′XX′, 2H, -C5H4), 4.17 (AA′XX′, 2H, -C5H4), 3.75 (s, 5H, Cp), 3.42 (AA′XX′, 2H, -C5H4), 1.63 (d, 3JP-H = 14.5 Hz, 18H, -Me). 13C{1H} NMR (CD2Cl2): δ 161.9 (q, 1JB-C = 49.7 Hz, no DEPT, BArF24), 134.9 (m, DEPT +, BArF24), 132.5 (s, DEPT +, -Ph), 130.3 (s, no DEPT, -Ph), 129.4 (d, 2JP-C = 11.4 Hz, DEPT +, -Ph), 129.0 (m, no DEPT, BArF24), 127.3 (d, 3JP-C = 10.4 Hz, DEPT +, -Ph), 124.7 (q, 1JF-C = 272.2 Hz, no DEPT, BArF24), 117.6 (m, DEPT +, BArF24), 77.4 (m, DEPT +, -C5H4), 77.1 (m, DEPT +, -C5H4), 75.7 (m, no DEPT, -C5H4), 73.3 (m, DEPT +, -C5H4), 71.4 (s, DEPT +, Cp), 70.8 (m, DEPT +, -C5H4), 42.4 (d, 1JP-C = 14.9 Hz, no DEPT, -CMe3), 32.1 (s, DEPT +, -Me). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 74.4 (dd, 2JP-P = 429.6 and 6.1 Hz, -PtBu2), 43.0 (dd, 2JP-P = 18.1 and 6.1, -PPh2), 22.8 (dd, 2JP-P = 429.6 and 18.1 Hz, -PPh2Fc). Anal. Calc. for C82H67BClF24Fe2P3Pd: C, 55.98; H, 3.84. Found: C, 56.11; H, 3.93%.
[Pd(dcpf)(PMe3)Cl][BArF24]
The product was isolated as an orange solid in 74% yield. 1H NMR (CD2Cl2) δ: 7.64 (br s, 8H, BArF24), 7.48 (br s, 4H, BArF24), 4.51 (AA′XX′, 2H, -C5H4), 4.49 (AA′XX′, 2H, -C5H4), 4.45 (m, 4H, -C5H4), 2.71 (m, 2H, -Cy), 2.03–1.04 (m, 40H, -Cy), 1.68 (d, 2JP-H = 11.1 Hz, 9H, -Me), 1.08 (m, 2H, -Cy). 13C{1H} NMR (CD2Cl2): δ 161.9 (q, 1JB-C = 49.7 Hz, no DEPT, BArF24), 134.9 (m, DEPT +, BArF24), 129.0 (m, no DEPT, BArF24), 124.7 (q, 1JF-C = 272.3 Hz, no DEPT, BArF24), 117.6 (m, DEPT +, BArF24), 77.0 (d, 1JP-C = 10.9 Hz, no DEPT, -C5H4), 76.5 (d, 1JP-C = 10.0 Hz, no DEPT, -C5H4), 74.9 (d, 2JP-C = 7.9 Hz, DEPT +, -C5H4), 74.3 (d, 3JP-C = 6.6 Hz, DEPT +, -C5H4), 73.4 (d, 3JP-C = 5.6 Hz, DEPT +, -C5H4), 73.2 (d, 3JP-C = 6.5 Hz, DEPT +, -C5H4), 39.0 (d, 1JP-C = 38.8 Hz, DEPT + -Cy), 37.8 (d, 1JP-C = 24.4 Hz, DEPT +, -Cy), 31.1 (d, 3JP-C = 11.0 Hz, DEPT -, -Cy), 30.7 (d, 3JP-C = 13.9 Hz, DEPT -, -Cy), 27.5 (dd, JP-C = 28.5 and 13.4 Hz, DEPT -, -Cy), 26.9 (dd, JP-C = 21.4 and 10.7 Hz, DEPT -, -Cy), 26.0 (s, DEPT -, -Cy), 25.6 (s, DEPT -, -Cy), 17.4 (dd, JP-C = 29.9 and 2.6 Hz, DEPT +, -Me). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 60.6 (dd, 2JP-P = 30.4 and 13.6, -PCy2), 50.2 (dd, 2JP-P = 443.0 and 13.6 Hz, -PCy2), −11.0 (dd, 2JP-P = 443.0 and 30.4 Hz, -PMe3). Anal. Calc. for C69H73BClF24FeP3Pd: C, 53.35; H, 4.74. Found: C, 53.04; H, 4.51%.
[Pd(dfurpf)(PMe3)Cl][BArF24]
The product was isolated as a red–orange solid in 86% yield. 1H NMR (CDCl3) δ: 7.64 (br s, 8H, BArF24), 7.44 (br s, 4H, BArF24), 6.99 (br s, 2H, -furanyl), 6.27 (br s, 2H, -furanyl), 6.12 (br s, 2H, -furanyl), 5.79 (br s, 2H, -furanyl), 4.44 (AA′XX′, 2H, -C5H4), 4.41 (AA′XX′, 2H, -C5H4), 4.34 (AA′XX′, 2H, -C5H4), 3.93 (AA′XX′, 2H, -C5H4), 2.14 (d, 2JP-H = 15.0 Hz, 9H, -Me), 1.19 (s, 12H, -Me). 13C{1H} NMR (CDCl3): δ 160.7 (q, 1JB-C = 49.5 Hz, no DEPT, BArF24), 158.3 (d, 1JP-C = 8.1 Hz, no DEPT, -furanyl), 139.0 (m, no DEPT, -furanyl), 133.6 (m, DEPT +, BArF24), 130.5 (d, 3JP-C = 2.9 Hz, DEPT +, -furanyl), 127.9 (m, no DEPT, BArF24), 125.2 (d, 2JP-C = 17.0 Hz, DEPT +, -furanyl), 124.8 (d, 2JP-C = 17.0 Hz, DEPT +, -furanyl), 123.5 (q, 1JF-C = 272.4 Hz, no DEPT, BArF24), 116.4 (m, DEPT +, BArF24), 108.0 (d, 3JP-C = 7.3 Hz, -furanyl), 107.4 (d, 3JP-C = 7.3 Hz, -furanyl), 75.1 (d, 2JP-C = 13.9 Hz, DEPT +, -C5H4), 74.1 (d, 2JP-C = 11.6 Hz, DEPT +, -C5H4), 73.7 (d, 3JP-C = 9.3 Hz, DEPT +, -C5H4), 73.4 (d, 3JP-C = 7.2 Hz, DEPT +, -C5H4), 28.7 (s, DEPT +, furanyl-CH3), 12.8 (d, 1JP-C = 60.1 Hz, DEPT +, -PCH3), 32.1 (s, DEPT +, -Me). 19F{1H} NMR (CDCl3): δ −62.4 (s). 31P{1H} NMR (CDCl3): δ 31.4 (dd, 2JP-P = 493.0 and 15.7, -PPh2), −5.9 (dd, 2JP-P = 15.7 and 12.9 Hz, -P(furanyl)2), −9.4 (dd, 2JP-P = 493.0 and 12.9 Hz, -P(furanyl)2. Anal. Calc. for C65H49BClF24FeO4P3Pd: C, 50.53; H, 3.20. Found: C, 50.34; H, 3.11%.
[Pd(dfurpf)(PPh3)Cl][BArF24]
The product was isolated as a red–orange solid in 57% yield. 1H NMR (CDCl2) δ: 7.65 (br s, 8H, BArF24), 7.50–7.20 (m, 19H, -Ph and BArF24), 6.99 (br s, 2H, -furanyl), 6.33 (br s, 2H, -furanyl), 6.16 (br s, 2H, -furanyl), 5.86 (br s, 2H, -furanyl), 4.44 (AA′XX′, 2H, -C5H4), 4.39 (AA′XX′, 4H, -C5H4), 4.01 (AA′XX′, 2H, -C5H4), 2.34 (s, 6H, -Me), 2.01 (s, 6H, -Me). 13C{1H} NMR (CD2Cl2): δ 161.9 (q, 1JB-C = 49.8 Hz, no DEPT, BArF24), 159.8 (d, 1JP-C = 5.9 Hz, no DEPT, -furanyl), 159.7 (d, 1JP-C = 6.6 Hz, no DEPT, -furanyl), 139.9 (m, DEPT +, BArF24), 135.4 (d, 2JP-C = 10.3 Hz, DEPT +, -Ph), 134.9 (s, DEPT +, -furanyl), 134.8 (s, DEPT +, -furanyl), 134.7 (s, DEPT +, -furanyl), 129.0 (m, no DEPT, BArF24), 128.6 (d, 3JP-C = 6.6 Hz, DEPT +, -Ph), 128.5 (s, DEPT +, -furanyl), 128.4 (s, DEPT +, -furanyl), 126.3 (d, 1JP-C = 16.7 Hz, no DEPT, -Ph), 126.0 (s, DEPT +, -Ph), 125.9 (m, DEPT +, -furanyl), 124.7 (q, 1JF-C = 272.2 Hz, no DEPT, BArF24), 117.6 (m, DEPT +, BArF24), 109.2 (s, DEPT +, -furanyl), 109.1 (s, DEPT +, -furanyl), 108.4 (s, DEPT +, -furanyl), 108.3 (s, DEPT +, -furanyl), 76.1 (d, 2JP-C = 13.9 Hz, DEPT +, -C5H4), 75.4 (d, 2JP-C = 11.3 Hz, DEPT +, -C5H4), 74.9 (d, 3JP-C = 9.4 Hz, DEPT +, -C5H4), 74.7 (d, 3JP-C = 7.4 Hz, DEPT +, -C5H4), 74.3 (m, no DEPT, -C5H4), 73.4 (m, no DEPT, -C5H4), 14.0 (s, DEPT +, furanyl-CH3), 13.5 (s, DEPT +, -furanyl-CH3). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 31.8 (dd, 2JP-P = 491.0 and 17.1, -PPh2Fc), −5.8 (dd, 2JP-P = 17.1 and 11.7 Hz, -P(furanyl)2), −9.0 (dd, 2JP-P = 491.0 and 11.7 Hz, -P(furanyl)2). Anal. Calc. for C80H52BClF24FeO4P3Pd: C, 55.94; H, 3.03. Found: C, 56.23; H, 2.94%.
[Pd(dfurpf)(PPh2Fc)Cl][BArF24]
The product was isolated as a dark red solid in 95% yield. 1H NMR (CDCl2) δ: 7.64 (br s, 8H, BArF24), 7.58–7.45 (m, 8H, -Ph and BArF24), 7.39 (t, 2H, JH-H = 7.5 Hz, -Ph), 7.28 (m, 4H, -Ph), 6.97 (br s, 2H, -furanyl), 6.45 (br s, 2H, -furanyl), 6.16 (br s, 2H, -furanyl), 5.89 (br s, 2H, -furanyl), 4.41 (AA′XX′, 2H, -C5H4), 4.36 (AA′XX′, 2H, -C5H4), 4.09 (AA′XX′, 2H, -C5H4), 4.01 (AA′XX′, 2H, -C5H4), 3.85 (s, 5H, -Cp), 2.36 (s, 6H, -Me), 2.03 (s, 6H, -Me). 13C{1H} NMR (CD2Cl2): δ 161.9 (q, 1JB-C = 50.0 Hz, no DEPT, BArF24), 159.7 (d, 1JP-C = 5.9 Hz, no DEPT, -furanyl), 159.4 (d, 1JP-C = 6.5 Hz, no DEPT, -furanyl), 134.9 (m, DEPT +, BArF24), 134.2 (s, DEPT +, -furanyl), 134.0 (s, DEPT +, -furanyl), 131.4 (s, DEPT +, -furanyl), 129.0 (m, no DEPT, BArF24), 128.2 (s, DEPT +, -furanyl), 128.1 (s, DEPT +, -furanyl), 125.9 (m, DEPT +, -furanyl), 124.7 (q, 1JF-C = 272.6 Hz, no DEPT, FArF24), 117.6 (m, DEPT +, BArF24), 109.1 (s, DEPT +, -furanyl), 109.0 (s, DEPT +, -furanyl), 108.4 (s, DEPT +, -furanyl), 108.3 (s, DEPT +, -furanyl), 75.9 (d, 2JP-C = 9.2 Hz, DEPT +, -C5H4), 75.3 (m, DEPT +, -C5H4), 74.7 (d, 3JP-C = 9.2 Hz, DEPT +, -C5H4), 74.4 (d, 3JP-C = 9.2 Hz, DEPT +, -C5H4), 71.4 (m, no DEPT, -C5H4), 70.7 (s, DEPT +, Cp), 14.0 (s, DEPT +, furanyl-CH3), 13.6 (s, DEPT +, -furanyl-CH3). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 30.1 (dd, 2JP-P = 500.8 and 15.6, -PPh2Fc), −5.9 (dd, 2JP-P = 17.6 and 15.6 Hz, -P(furanyl)2), −10.6 (dd, 2JP-P = 500.8 and 17.3 Hz, -P(furanyl)2). Anal. Calc. for C84H59BClF24Fe2O4P3Pd: C, 57.77; H, 3.41. Found: C, 57.44; H, 3.42%.
[Pd(dppf)(P(NMe2)3)Cl][BArF24]
The product was isolated as a red solid in 86% yield. 1H NMR (CD2Cl2) δ: 8.06–7.06 (m, 32H, -Ph and BArF24), 4.65 (AA′XX′, 2H, -C5H4), 4.59 (AA′XX′, 2H, -C5H4), 4.13 (AA′XX′, 2H, -C5H4), 3.18 (AA′XX′, 2H, -C5H4), 2.56 (s, 18H, -Me). 13C{1H} NMR (CD2Cl2): δ 161.9 (q, 1JB-C = 51.1 Hz, no DEPT, BArF24), 134.9 (m, DEPT +, BArF24), 132.4 (s, DEPT +, -Ph), 131.4 (s, DEPT +, -Ph), 128.9 (m, DEPT +, -Ph and BArF24), 124.7 (q, 1JF-C = 272.2 Hz, no DEPT, BArF24), 117.6 (m, DEPT +, BArF24), 77.6 (d, 1JP-C = 12.6 Hz, DEPT +, -C5H4), 76.4 (m, no DEPT, -C5H4), 75.7 (d, 2JP-C = 6.8 Hz, DEPT +, -C5H4), 75.3 (d, 2JP-C = 5.9 Hz, DEPT +, -C5H4), 73.9 (d, 3JP-C = 5.5 Hz, no DEPT, -C5H4), 40.1 (d, 2JP-C = 7.8 Hz, DEPT +, -Me). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 94.3 (dd, 2JP-P = 607.0 and 10.0 Hz, -P(NMe2)3), 32.2 (dd, 2JP-P = 17.5 and 9.9, -PPh2), 19.0 (dd, 2JP-P = 607.0 and 17.5 Hz, -PPh2). Anal. Calc. for C52H58BClF24FeN3P3Pd: C, 45.39; H, 4.25. Found: C, 45.01; H, 3.99%.
[Pd(dppf)(PiPr3)Cl][BArF24]
The product was isolated as a red solid in 75% yield. 1H NMR (CD2Cl2) δ: 7.73 (dd, JH-H = 11.4 and 7.7 Hz, 4H, -Ph), 7.64 (m, 8H, BArF24), 7.48 (m, 4H, BArF24), 7.45 (m, 12H, -Ph), 7.16 (t, JH-H = 8.2 Hz, -Ph), 4.89 (AA′XX′, 2H, -C5H4), 4.68 (AA′XX′, 2H, -C5H4), 4.23 (AA′XX′, 2H, -C5H4), 3.00 (AA′XX′, 2H, -C5H4), 2.11 (m, 3H, -CHMe2). 1.17 (d, JH-H = 14.7 Hz, -Me), 1.15 (d, JH-H = 14.7 Hz, -Me). 13C{1H} NMR (CD2Cl2): δ 161.7 (q, 1JB-C = 49.9 Hz, no DEPT, BArF24), 134.7 (m, DEPT +, BArF24), 134.6 (s, DEPT +, -Ph), 134.5 (s, DEPT +, -Ph), 133.4 (d, 1JP-C = 53.5 Hz, no DEPT, -Ph), 132.9 (d, 3JP-C = 2.6 Hz, DEPT +, -Ph), 131.4 (d, 3JP-C = 2.6 Hz, DEPT +, -Ph), 129.0 (m, no DEPT, BArF24), 128.8 (d, 2JP-C = 11.3 Hz, DEPT +, -Ph), 128.6 (d 2JP-C = 10.6 Hz, DEPT +, -Ph), 128.6 (d 2JP-C = 11.6 Hz, DEPT +, -Ph), 124.6 (q, 1JF-C = 272.6 Hz, no DEPT, BArF24), 117.4 (m, DEPT +, BArF24), 79.0 (d, 2JP-C = 13.8 Hz, DEPT +, -C5H4), 76.0 (d, 3JP-C = 8.0 Hz, DEPT +, -C5H4), 75.5 (d, 2JP-C = 8.8 Hz, DEPT +, -C5H4), 74.2 (d, 3JP-C = 5.8 Hz, DEPT +, -C5H4), 68.4 (d, 1JP-C = 46.4Hz, no DEPT, -C5H4), 24.8 (d, 1JP-C = 20.5 Hz, DEPT +, -CHMe2), 20.3 (s, DEPT +, -Me). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 50.6 (dd, 2JP-P = 450.0 and 17.6 Hz, -PiPr3), 32.7 (dd, 2JP-P = 17.6 and 5.9, -PPh2), 21.6 (dd, 2JP-P = 450.0 and 5.9 Hz, -PPh2). Anal. Calc. for C75H61BClF24FeP3Pd: C, 55.83; H, 3.81. Found: C, 56.02; H, 3.97%.
[Pd(dppf)(P(CH2Ph)3)Cl][BArF24]
The product was isolated as an orange–red solid in 84% yield. 1H NMR (CD2Cl2) δ: 7.86–6.94 (m, 47H, -Ph and BArF24), 4.41 (AA′XX′, 2H, -C5H4), 4.37 (AA′XX′, 2H, -C5H4), 3.99 (AA′XX′, 2H, -C5H4), 3.80 (AA′XX′, 2H, -C5H4), 2.93 (d, 2JP-H = 9.4 Hz, 6H, -CH2Ph). 13C{1H} NMR (CD2Cl2): δ 161.9 (q, 1JB-C = 50.0 Hz, no DEPT, BArF24), 134.9 (m, DEPT +, BArF24), 134.6 (d, 2JP-C = 10.9 Hz, DEPT +, -Ph), 134.4 (d, 2JP-C = 12.5 Hz, DEPT +, -Ph), 133.2 (m, no DEPT, -Ph), 133.2 (s, DEPT +, -Ph), 132.0 (d, 3JP-C = 2.8 Hz, -Ph), 131.2 (m, no DEPT, -Ph), 130.4 (d, 3JP-C = 5.3 Hz, DEPT +, -Ph), 129.6 (d, 2JP-C = 11.6 Hz, -Ph), 129.4 (d, 3JP-C = 2.2 Hz, DEPT +, -Ph), 129.0 (m, no DEPT, BArF24), 128.8 (d, 2JP-C = 10.8 Hz, DEPT +, -Ph), 128.5 (m, no DEPT, -Ph), 127.9 (d, 3JP-C = 2.9 Hz, -Ph), 124.7 (q, 1JF-C = 272.3 Hz, no DEPT, BArF24), 117.6 (m, DEPT +, BArF24), 77.2 (d, 2JP-C = 12.3 Hz, DEPT +, -C5H4), 76.8 (d, 2JP-C = 10.0 Hz, DEPT +, -C5H4), 75.1 (d, 3JP-C = 2.2 Hz, DEPT +, -C5H4), 75.0 (d, 3JP-C = 4.1 Hz, DEPT +, -C5H4), 69.7 (m, no DEPT, -C5H4), 69.2 (m, no DEPT, -C5H4), 29.4 (dd, J = 19.9 and 2.9 Hz, DEPT -, -CH2Ph). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 34.0 (dd, 2JP-P = 16.0 and 6.5 Hz, -PPh2), 30.1 (dd, 2JP-P = 452.4 and 6.5, -PPh2), 18.9 (dd, 2JP-P = 452.4 and 16.0 Hz, -PPh3). Anal. Calc. for C87H61BClF24FeP3Pd: C, 59.46; H, 3.50. Found: C, 59.14; H, 3.65%.
[Pd(dppf)(P(m-tolyl)3)Cl][BArF24]
The product was isolated as an orange–red solid in 72% yield. 1H NMR (CD2Cl2) δ: 8.03–7.00 (m, 44H, -Ph, -tol, and BArF24), 4.74 (AA′XX′, 2H, -C5H4), 4.67 (AA′XX′, 2H, -C5H4), 4.36 (AA′XX′, 2H, -C5H4), 3.55 (AA′XX′, 2H, -C5H4), 2.23 (s, 9H, -CH3). 13C{1H} NMR (CD2Cl2): δ 161.9 (q, 1JB-C = 49.9 Hz, no DEPT, BArF24), 138.6 (s, DEPT +, -Ph), 138.5 (s, DEPT +, -Ph), 134.7 (m, DEPT +, BArF24), 134.2 (m, no DEPT, -Ph), 132.1 (d, 3JP-C = 2.8 Hz, DEPT +, -Ph), 131.7 (d, 3JP-C = 2.6 Hz, DEPT +, -Ph), 131.4 (s, DEPT +, -Ph), 130.5 (m, no DEPT, -Ph), 129.2 (d, 2JP-C = 10.1 Hz, DEPT +, -Ph), 129.0 (m, no DEPT, BArF24), 128.7 (d 2JP-C = 9.8 Hz, DEPT +, -Ph), 128.6 (d 2JP-C = 11.6 Hz, DEPT +, -Ph), 128.2 (m, no DEPT, -Ph), 125.6 (m, DEPT +, -Ph), 124.7 (q, 1JF-C = 272.3 Hz, no DEPT, BArF24), 117.6 (m, DEPT +, BArF24), 77.6 (d, 2JP-C = 12.3 Hz, DEPT +, -C5H4), 76.0 (d, 2JP-C = 12.3 Hz, no DEPT, -C5H4), 76.0 (d, 3JP-C = 8.1 Hz, DEPT +, -C5H4), 75.4 (d, 2JP-C = 8.1 Hz, DEPT +, -C5H4), 74.6 (d, 3JP-C = 6.1 Hz, DEPT +, -C5H4), 21.2 (s, DEPT +, -CH3). 19F{1H} NMR (CD2Cl2): δ −62.9 (s). 31P{1H} NMR (CD2Cl2): δ 35.2 (dd, 2JP-P = 17.5 and 5.8 Hz, -PPh2), 30.2 (dd, 2JP-P = 478.7 and 17.5, -P(m-tol)3), 26.5 (dd, 2JP-P = 478.7 and 5.8 Hz, -PPh2). Anal. Calc. for C87H64BClF24FeP3Pd: C, 59.35; H, 3.66. Found: C, 59.28; H, 3.72%.
[Pd(dppf)(P(p-tolyl)3)Cl][BArF24]
The product was isolated as an orange–red solid in 88% yield. 1H NMR (CD2Cl2) δ: 7.89–6.91 (m, 44H, -Ph, -tol, and BArF24), 4.56 (AA′XX′, 2H, -C5H4), 4.51 (AA′XX′, 2H, -C5H4), 4.23 (AA′XX′, 2H, -C5H4), 3.50 (AA′XX′, 2H, -C5H4), 2.24 (s, 9H, -CH3). 13C{1H} NMR (CD2Cl2): δ 161.7 (q, 1JB-C = 49.6 Hz, no DEPT, BArF24), 142.3 (s, DEPT +, -Ph), 134.7 (m, DEPT +, BArF24), 134.2 (m, no DEPT, -Ph), 132.1 (d, 3JP-C = 2.8 Hz, DEPT +, -Ph), 131.7 (d, 3JP-C = 2.6 Hz, DEPT +, -Ph), 131.4 (s, DEPT +, -Ph), 130.5 (m, no DEPT, -Ph), 129.2 (d, 2JP-C = 10.1 Hz, DEPT +, -Ph), 129.0 (m, no DEPT, BArF24), 128.7 (d 2JP-C = 9.8 Hz, DEPT +, -Ph), 128.6 (d 2JP-C = 11.6 Hz, DEPT +, -Ph), 128.2 (m, no DEPT, -Ph), 125.6 (m, DEPT +, -Ph), 124.6 (q, 1JF-C = 272.3 Hz, no DEPT, BArF24), 117.5 (m, DEPT +, BArF24), 77.3 (d, 2JP-C = 12.0 Hz, DEPT +, -C5H4), 76.5 (m, no DEPT, -C5H4), 75.8 (d, 3JP-C = 8.2 Hz, DEPT +, -C5H4), 75.2 (d, 2JP-C = 9.7 Hz, DEPT +, -C5H4), 74.4 (d, 3JP-C = 5.6 Hz, DEPT +, -C5H4), 75.2 (m, no DEPT, -C5H4), 21.1 (s, DEPT +, -CH3). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 35.2 (dd, 2JP-P = 17.6 and 5.9 Hz, -PPh2), 30.3 (dd, 2JP-P = 479.3 and 17.6, -P(p-tol)3), 26.5 (dd, 2JP-P = 479.3 and 5.9 Hz, -PPh2). Anal. Calc. for C87H64BClF24FeP3Pd: C, 59.35; H, 3.66. Found: C, 59.28; H, 3.72%.
[Pd(dppf)(P(p-C6H4OMe)3)Cl][BArF24]
The product was isolated as an orange–red solid in 45% yield. 1H NMR (CD2Cl2) δ: 7.90–6.98 (m, 44H, -Ph, -C6H4OMe, and BArF24), 4.53 (AA′XX′, 2H, -C5H4), 4.50 (AA′XX′, 2H, -C5H4), 4.23 (AA′XX′, 2H, -C5H4), 3.70 (s, 9H, -OCH3), 3.54 (AA′XX′, 2H, -C5H4). 13C{1H} NMR (CD2Cl2): δ 162.2 (d, 4JP-C = 1.5 Hz, no DEPT, -OCH3), 161.9 (q, 1JB-C = 49.8 Hz, no DEPT, BArF24), 136.1 (d, 3JP-C = 4.4 Hz, DEPT +, -Ph), 136.0 (d, 3JP-C = 4.4 Hz, DEPT +, -Ph), 134.9 (m, DEPT +, BArF24), 134.2 (d, 2JP-C = 12.1 Hz, DEPT +, -Ph), 132.3 (d, 3JP-C = 2.9 Hz, DEPT +, -Ph), 131.8 (s, DEPT +, -Ph), 130.8 (m, no DEPT, -Ph), 129.2 (m, no DEPT, BArF24), 128.9 (d, 2JP-C = 3.3 Hz, DEPT +, -Ph), 128.8 (d, 2JP-C = 11.6 Hz, DEPT +, -Ph), 124.7 (q, 1JF-C = 272.3 Hz, no DEPT, BArF24), 120.1 (m, no DEPT, -Ph), 117.6 (m, DEPT +, BArF24), 114.2 (d, 3JP-C = 3.2 Hz, DEPT +, -Ph), 114.1 (d, 3JP-C = 3.4 Hz, DEPT +, -Ph), 77.3 (d, 2JP-C = 12.1 Hz, DEPT +, -C5H4), 76.0 (d, 3JP-C = 6.8 Hz, DEPT +, -C5H4), 75.3 (d, 2JP-C = 8.2 Hz, DEPT +, -C5H4), 74.5 (d, 3JP-C = 5.0 Hz, DEPT +, -C5H4), 69.8 (m, no DEPT, -C5H4), 69.1 (m, no DEPT, -C5H4), 68.2 (s, DEPT +, -OCH3). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 50.5 (dd, 2JP-P = 451.9 and 17.7 Hz, -P(p-C6H4OMe)3), 32.6 (dd, 2JP-P = 17.7 and 6.3, -PPh2), 21.6 (dd, 2JP-P = 451.9 and 6.3 Hz, -PPh2). Anal. Calc. for C87H64BClF24FeO3P3Pd: C, 57.78; H, 3.57. Found: C, 58.09; H, 3.71%.
[Pd(dppf)(P(p-C6H4F)3)Cl][BArF24]
The product was isolated as an orange–red solid in 75% yield. 1H NMR (CD2Cl2) δ: 7.90–6.78 (m, 44H, -Ph, -C6H4F, and BArF24), 4.48 (m, 4H, -C5H4), 4.28 (AA′XX′, 2H, -C5H4), 3.69 (AA′XX′, 2H, -C5H4). 13C{1H} NMR (CD2Cl2): δ 163.6 (d, 1JF-C = 248.6 Hz, no DEPT, CF), 161.9 (q, 1JB-C = 49.6 Hz, no DEPT, BArF24), 134.9 (m, DEPT +, BArF24), 133.9 (d, 2JP-C = 12.2 Hz, DEPT +, -Ph), 132.9 (m, DEPT +, -Ph), 132.2 (s, DEPT +, -Ph), 131.8 (s, DEPT +, -Ph), 130.1 (m, no DEPT, -Ph), 129.2 (m, no DEPT, BArF24), 128.9 (d, 2JP-C = 3.3 Hz, DEPT +, -Ph), 128.8 (m, no DEPT +, -Ph), 124.7 (q, 1JF-C = 272.2 Hz, no DEPT, BArF24), 124.3 (m, no DEPT, -Ph), 117.6 (m, DEPT +, BArF24), 116.3 (dd, J = 21.9 and 7.5 Hz, DEPT +, -Ph), 115.9 (dd, J = 21.1 and 7.5 Hz, DEPT +, -Ph), 77.1 (d, 2JP-C = 11.9 Hz, DEPT +, -C5H4), 76.5 (m, no DEPT, -C5H4), 76.2 (d, 3JP-C = 6.8 Hz, DEPT +, -C5H4), 75.9 (m, no DEPT, -C5H4), 75.6 (d, 2JP-C = 8.2 Hz, DEPT +, -C5H4), 74.9 (d, 3JP-C = 5.9 Hz, DEPT +, -C5H4). 19F{1H} NMR (CD2Cl2): δ −62.8 (s, BArF24), −106.7 (s, -C6H4F). 31P{1H} NMR (CD2Cl2): δ 36.5 (dd, 2JP-P = 18.2 and 6.4 Hz, -PPh2), 30.4 (dd, 2JP-P = 486.7 and 6.4, -P(p-C6H4F)3), 26.1 (dd, 2JP-P = 486.7 and 18.2 Hz, -PPh2). Anal. Calc. for C84H55BClF27FeP3Pd: C, 56.92; H, 3.13. Found: C, 57.07; H, 3.01%.
[Pd(dfurpf)(P(p-C6H4CF3)3)Cl][BArF24]
The product was isolated as an orange–red solid in 67% yield. 1H NMR (CDCl2) δ: 7.64 (br s, 8H, BArF24), 7.58–7.32 (m, 16H, -C6H4CF3 and BArF24), 6.96 (br s, 2H, -furanyl), 6.47 (br s, 2H, -furanyl), 6.19 (br s, 2H, -furanyl), 5.94 (br s, 2H, -furanyl), 4.45 (m, 4H, -C5H4), 4.22 (m, 4H, -C5H4), 2.33 (s, 6H, -Me), 2.08 (s, 6H, -Me). 13C{1H} NMR (CD2Cl2): δ 161.7 (q, 1JB-C = 49.8 Hz, no DEPT, BArF24), 160.3 (d, 1JP-C = 6.1 Hz, no DEPT, -furanyl), 159.9 (d, 1JP-C = 6.5 Hz, no DEPT, -furanyl), 139.6 (m, DEPT +, BArF24), 135.0 (d, 2JP-C = 11.4 Hz, DEPT +, -Ph), 134.2 (s, DEPT +, -furanyl), 134.0 (s, DEPT +, -furanyl), 133.5 (s, DEPT +, -furanyl), 132.6 (d, 1JP-C = 48.3 Ha, no DEPT, -Ph), 131.2 (q, 1JF-C = 32.51 Hz, no DEPT, -CF3), 128.8 (m, no DEPT, BArF24), 126.5 (d, 3JP-C = 16.4 Hz, DEPT +, -Ph), 126.3 (s, DEPT +, -furanyl), 126.1 (s, DEPT +, -furanyl), 125.6 (m, DEPT +, -furanyl), 124.6 (s, DEPT +, -Ph), 124.6 (q, 1JF-C = 272.4 Hz, no DEPT, BArF24), 122.9 (d, 1JP-C = 74.3 Hz, no DEPT, -Ph), 117.5 (m, DEPT +, BArF24), 109.5 (s, DEPT +, -furanyl), 109.4 (s, DEPT +, -furanyl), 108.7 (s, DEPT +, -furanyl), 108.7 (s, DEPT +, -furanyl), 75.9 (d, 2JP-C = 12.7 Hz, DEPT +, -C5H4), 75.7 (d, 2JP-C = 14.0 Hz, DEPT +, -C5H4), 75.2 (d, 3JP-C = 9.5 Hz, DEPT +, -C5H4), 75.1 (d, 3JP-C = 8.1 Hz, DEPT +, -C5H4), 72.4 (m, no DEPT, -C5H4), 69.2 (m, no DEPT, -C5H4), 13.9 (s, DEPT +, furanyl-CH3), 13.5 (s, DEPT +, -furanyl-CH3). 19F{1H} NMR (CD2Cl2): δ −62.8 (s, BArF24), −63.7 (s, -CF3). 19F{1H} NMR (CD2Cl2): δ −62.8 (s). 31P{1H} NMR (CD2Cl2): δ 28.0 (dd, 2JP-P = 495.2 and 19.6, -P(p-C6H4CF3)3), −5.2 (dd, 2JP-P = 19.6 and 6.0 Hz, -P(furanyl)2), −6.4 (dd, 2JP-P = 495.2 and 6.0 Hz, -P(furanyl)2). Anal. Calc. for C83H52BClF33FeO4P3Pd: C, 51.51; H, 2.71. Found: C, 51.14; H, 2.94%.