Synthesis of 2

Ligand 1b (23 mg, 2.2 × 10^–5 mol) and [Rh(CO)₂Cl]₂ (8.5 mg, 2.2 × 10^–5 mol) were dissolved in 15 mL of toluene. Nitrogen was bubbled through the mixture for 15 min, and the solution was refluxed for another 30 min. The solvent was evaporated and the products were purified by column chromatography on SiO₂ with CH₂Cl₂; 2 was eluted as the second brown band (16% yield). ¹H NMR (CD₂Cl₂, 300 K, 600 MHz): δ 13.09 (br s, 1H, NH), 7.63 (m, 3H, rhodacycle*, o-Anis), 7.54 (m, 2H, o-Ph), 7.45 (m, 3H, rhodacycle*, o-Anis), 7.39–7.29 (m, 13H, o/m/p-Ph), 7.24 (m, 4H, pyrr, o/m-Ph), 7.18 (m, 3H, tell, m-Ph), 7.09 (m, 2H, m-Anis), 7.06 (d, ³J_HH = 4.6 Hz, 1H, pyrr), 7.00 (m, 2H, m-Anis), 6.63 (dd, ³J_HH = 4.3 Hz, ⁴J_HH = 2.5 Hz, 1H, pyrr), 6.26 (d, ³J_HH = 4.9 Hz, 1H, tell), 6.20 (dd, ³J_HH = 4.3 Hz, ⁴J_HH = 2.5 Hz, 1H, pyrr), 3.90 (s, 3H, OMe), 3.89 (s, 3H, OMe); ¹³C NMR (CD₂Cl₂, 300 K, 150 MHz): δ 215.3 (d, ¹J_RhC = 27 Hz, α-rhodacycle), 182.7 (d, ¹J_RhC = 31 Hz, α-rhodacycle), 178.3 (meso), 177.9 (α-tell), 176.7 (β-rhodacycle), 164.7 (para), 161.5 (para), 160.6 (α-tell), 159.3 (α-pyrr), 157.4 (α-pyrr), 155.7 (α-pyrr), 155.3 (meso), 149.1 (β-rhodacycle), 146.0 (ipso), 145.9 (ipso), 143.2 (ipso), 141.6 (ipso), 141.3 (β-pyrr), 138.1 (β-pyrr), 137.8 (α-pyrr), 135.5 (β-tell), 133.6 (ipso), 132.7 (o-Anis), 131.3 (m-Ph) 130.8 (o/m-Ph), 130.2 (o-Anis), 130.0 (Ph), 129.5 (β-pyrr), 129.0 (β-tell), 128.9 (Ph), 128.8 (Ph), 128.7 (Ph), 128.6 (Ph), 128.3 (Ph), 128.2 (Ph), 128.0 (Ph), 127.9 (Ph), 126.5 (ipso), 119.1 (β-pyrr), 114.6 (m-Anis), 114.4 (m-Anis), 64.3 (meso), 62.3 (meso), 56.3 (OMe), 56.0 (OMe); UV–vis (nm, log ε) = 879 (3.9), 471 (4.1), 315 (4.1); HRMS (ESI) m/z: 1125.0716, calcd for C₅₈H₄₃Cl₂N₂O₂Rh¹³⁰Te, [M + Na]⁺: 1125.0712. *¹⁰³Rh splitting of the rhodacyclopentadiene signals was detected in following conditions: C₆D₆, 350 K, 600 MHz: 7.76 (dd, ³J_RhH = 1.2 Hz, ³J_HH = 3.9 Hz), 7.63 (dd, ³J_RhH = 1.4 Hz, ³J_HH = 3.9 Hz). Crystal data for compound 2: C₅₈H₄₃Cl₂N₂O₂RhTe, 2(CHCl₃), M = 1340.09, monoclinic, P2₁/c, a = 11.759(3) Å, b = 20.403(3) Å, c = 23.040(4) Å, β = 98.85(2)°, V = 5461.9(19) ų, Z = 4, D_c = 1.630 Mg m^–3, T = 100(2) K, R = 0.0475, wR = 0.1158 [6762 reflections with I > 2σ(I)] for 667 variables, CCDC 2214347.