<p>This journal is © The Royal Society of Chemistry 2000</p><p>Supplementary Information</p><p>Inner C-arylation of doubly N-confused porphyrin-Pd complex in toluene ---</p><p>A possibility of Pd3+ intermediate.</p><p>Hiroyuki Furutaa,b*, Hiromitsu Maedaa, Atsuhiro Osukaa*, Mikio Yasutakec, Teruo</p><p>Shinmyozuc and Yuichi Ishikawac</p><p> aDepartment of Chemistry, Graduate School of Science,</p><p>Kyoto University, Kyoto 606-8502, Japan</p><p> bPRESTO, JST</p><p> cInstitute for Fundamental Research of Organic Chemistry,</p><p>Kyushu University, Fukuoka 812-8581, Japan</p><p>Synthetic procedures of Pd(II)-N2CP-tolyl (2) </p><p>1 13 H, CNMR spectra of Pd(II)-N2CP-tolyl (2) </p><p>View of C53H18F20N4OPd·0.5C6H14·0.3H2O, Pd(II)-N2CP-tolyl (2)</p><p>Unit cell packing diagram for Pd(II)-N2CP-tolyl (2)</p><p>S1 This journal is © The Royal Society of Chemistry 2000</p><p>Synthetic Procedures for Pd(II)-N2CP-tolyl (2)</p><p>Pd(II) Complex of 2-Ethoxy-5,10,15,20-Tetrakis(pentafluorophenyl)-21-(3’-</p><p>Tolyl)-3,7-Diaza-21,22-Dicarbaporphyrin (Pd(II)-N2CP-m-tolyl, 2-meta) and </p><p>2-Ethoxy-5,10,15,20-Tetrapentafluorophenyl-21-(4’-Tolyl)-3,7-Diaza-21,22-</p><p>Dicarbaporphyrin (Pd(II)-N2CP-p-tolyl, 2-para). </p><p>To a toluene (70 ml) solution of ethoxy substituted tetrakis(pentafluorophenyl)-</p><p>1 N2CP (1) (20.4 mg, 0.02 mmol), Pd(OAc)2 (9.4 mg, 0.04 mmol) was added and stirred for 5 h at reflux temperature. The solvent was removed by evaporation and the residues were purified by silica gel column (Wakogel C-</p><p>200) with CH2Cl2 as an eluent. Recrystallization from hexane/CH 2Cl2 gave a mixture of the tolyl complex, 2-meta (12%) and 2-para (6%) as green solids.</p><p>The two isomers, 2-meta and 2-para, were unable to separate. 2-meta:</p><p>1 HNMR (CD2Cl2, 500 MHz, 27ºC):  (ppm) 10.42 (br, 1H, outer NH), 7.73 (d, J</p><p>= 5.0 Hz, 1H, H), 7.61 (d, J = 5.0 Hz, 1H, H), 7.52 (d, J = 5.0 Hz, 1H, H),</p><p>7.41 (d, J = 5.0 Hz, 1H, H), 7.34 (s, 1H, H), 6.36 (d, J = 4.5 Hz, 2H, Ar),</p><p>5.78 (br, 1H, Ar), 5.61 (br, 1H, Ar), 4.55 (q, J = 7.5 Hz, 1H, CH3CH 2 O), 4.38 (q,</p><p>J = 7.5 Hz, 1H, CH3CH 2 O), 1.80 (s, 3H, tolyl-CH3), 1.20 (t, J = 7.5 Hz, 3H,</p><p>1 CH 3 CH2O). 2-para: HNMR (CD2Cl2, 500 MHz, 27ºC):  (ppm) 10.42 (br, 1H, outer NH), 7.72 (d, J = 5.0 Hz, 1H, H), 7.61 (d, J = 5.0 Hz, 1H, H), 7.50 (d, J</p><p>= 5.0 Hz, 1H, H), 7.40 (d, J = 5.0 Hz, 1H, H), 7.31 (s, 1H, H), 6.35 (d, J =</p><p>8.0 Hz, 2H, Ar), 5.81 (d, J = 8.0 Hz, 2H, Ar), 4.55 (q, J = 7.5 Hz, 1H,</p><p>CH3CH 2 O), 4.38 (q, J = 7.5 Hz, 1H, CH3CH 2 O), 1.85 (s, 3H, tolyl-CH3), 1.20 (t,</p><p>S2 This journal is © The Royal Society of Chemistry 2000</p><p>J = 7.5 Hz, 3H, CH 3 CH2O).</p><p>13 CNMR (CD2Cl2, 500 MHz, 27ºC, a mixture of 2-meta and 2-para):  (ppm) </p><p>180.19, 180.04, 166.60, 154.49, 152.47, 150.37, 146.65, 146.02, 145.17, </p><p>144.08, 143.31, 138.18, 136.94, 136.32, 132.90, 131.43, 130.88, 129.87, </p><p>128.79, 127.23, 126.85, 126.38, 125.21, 123.89, 115.82, 113.88, 113.02, </p><p>110.54, 110.38, 97.73, 65.89, 20.31, 19.69, 13.40. Pentafluorophenyl signals </p><p>13 19 were unable to assign due to the multiple coupling of C- F. UV/vis (CHCl3): </p><p>-4 max[nm] (×10 ) 318.0 (3.1), 410.0 (3.0), 662.0 (1.5). FABMS: m/z (% intensity) = 1211.8 (100, M+).</p><p>1. H. Furuta, H. Maeda and A. Osuka, J. Am. Chem. Soc. 2000, 122, 803. </p><p>S3 This journal is © The Royal Society of Chemistry 2000</p><p>S4 This journal is © The Royal Society of Chemistry 2000</p><p>Supplementary Figure 3. View of C53H18F20N4OPd·0.5C6H14·0.3H2O, Pd(II)- N2CP-tolyl (2), showing the atom labelling scheme. Thermal ellipsoids are scaled to the 50% probability level. Hydrogen atoms shown are drawn to an arbitary scale.</p><p>S5 This journal is © The Royal Society of Chemistry 2000</p><p>Supplementary Figure 4. Unit cell packing diagram for Pd(II)-N2CP-tolyl (2).</p><p>S6</p>