10.1021/ic961304i.s001 Shwu-Juian Lin Shwu-Juian Lin Tay-Ning Hong Tay-Ning Hong Jo-Yu Tung Jo-Yu Tung Jyh-Horung Chen Jyh-Horung Chen Molecular Structures of Ge(tpp)(OAc)<sub>2</sub> and In(tpp)(OAc) and Their Implications:  Correlations between the <sup>13</sup>C NMR Chemical Shift of the Acetato Ligand and Different Types of Carboxylate Coordination in M(por)(OAc)<i><sub>n</sub></i> {por = tpp (5,10,15,20-Tetraphenylporphyrinate), tmpp (5,10,15,20-Tetrakis(4-methoxyphenyl)porphyrinate), tpyp (5,10,15,20-Tetrakis(4-pyridyl)porphyrinate); M = Ga, In, Tl, Ge, Sn; <i>n</i> = 1, 2} American Chemical Society 1997 13 C chemical shifts Molecular Structures Carboxylate Coordination unidentate case title compound Different Types germanium atom 13 C NMR Chemical Shift Ge Experimental results apical site acetato ligand 1.999 Å. carbonyl carbons 13 C methyl acetato group octahedral coordination geometry porphyrin plane acetate groups germanium center 13 C NMR data crystal structure chelating bidentate case carbonyl chemical shifts Acetato Ligand bidentate OAc carboxylate coordination 0.762 Å coordination sphere 1997-08-27 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Molecular_Structures_of_Ge_tpp_OAc_sub_2_sub_and_In_tpp_OAc_and_Their_Implications_Correlations_between_the_sup_13_sup_C_NMR_Chemical_Shift_of_the_Acetato_Ligand_and_Different_Types_of_Carboxylate_Coordination_in_M_por_OAc_i_sub_n_sub_i_por_tpp_5_10_15_20/3617787 In this work, we determine the crystal structure of bis(acetato)(<i>meso</i>-tetraphenylporphyrinato)germanium(III), Ge(tpp)(OAc)<sub>2</sub>. Experimental results indicate that the germanium atom has an octahedral coordination geometry. The geometry around the germanium center of the Ge(tpp)(OAc)<sub>2</sub> molecule has Ge−O(1) = 1.874(5) Å and an average Ge−N = 1.999 Å. The acetate groups are unidentately coordinated to the germanium(IV) atom. In the title compound, (acetato)(<i>meso</i>-tetraphenylporphyrinato)indium(III), In(tpp)(OAc), the coordination sphere of the In<sup>3+</sup> ion is an approximately square-based pyramid in which the apical site is occupied by an asymmetric (chelating) bidentate OAc<sup>-</sup> group. The average In−N bond distance is 2.173(3) Å, and the In atom is displaced 0.762 Å from the porphyrin plane. The In−O(1) and In−O(2) distances are 2.322(4) and 2.215(4) Å, respectively. To develop the correlations between the <sup>13</sup>C chemical shifts of the acetato ligand and types of carboxylate coordination, this work also thoroughly examines the <sup>13</sup>C NMR data of the methyl and carbonyl carbons on 13 acetato porphyrinato metal complexes M(por)(OAc)<i><sub>n</sub></i> with <i>n</i> = 1, 2, por = tpp, tmpp (5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinate), tpyp (5,10,15,20-tetrakis(4-pyridyl)porphyrinate), and M = Ga, In, Tl, Ge, Sn. According to these results, the <sup>13</sup>C methyl and carbonyl chemical shifts of the acetato group at 24 °C are separately located at 20.5 ± 0.2 and 168.2 ± 1.7 ppm for the acetate, which is unidentately coordinated to the metal (<i>i.e.,</i> the unidentate case) and at 18.0 ± 0.7 and 175.2 ± 1.6 ppm for the chelating bidentate case.