Feng-Ling Liao

Crystal of meso-p-tolyl-porphyrinato copper(II) Cu(tptp) and di-cation ion-pair complex [H4tptp]2+[CF3SO3]2− formation during the reaction of Cu(CF3SO3)2 with meso-p-tolyl-porphyrin in CDCl3

Abstract In the NMR and ESR time-scale of this experiment, an attempt was made to prepare the copper sitting-atop (SAT) species [Cu(H2tptp)]2+ by the reaction of Cu(CF3SO3)2 with meso-p-tolyl-porphyrin (H2tptp) in CDCl3; however, this led to the formation of meso-p-tolyl-porphyrinatocopper(II) Cu(tptp) and the protonated porphyrin [H4tptp]2+[CF3SO3]2− (2a). Previous researchers might have misinterpreted the SAT [Cu(H2tpp)]2+ complex as being a single component instead of a mixture of [H4tpp]2+[CF3SO3]2− (1) and Cu(tpp) for a similar reaction between 5,10,15,20-tetraphenylporphyrin H2tpp and Cu(CF3SO3)2 in CH3CN. This work determines the crystal structure of Cu(tptp) and its hyperfine constants aCu=94.0 G and aN=15.8 G using ESR. The crystal structure of [H4tptp]2+[CH3SO3]2− (3) is reported and employed to simulate the groupings of [H4tptp]2+ and CF3SO3− in the di-cation ion-pair complex 2a.

Preparation and structural characterization of mercury 21-thiaporphyrin complex: Hg II (Stpp)Cl ( Stpp=tetraphenyl -21-thiaporphyrin anion)

Abstract Treatment of tetraphenyl-21-thiaporphyrin (StppH) with Hg(OAc)2 in CH2Cl2 yields diamagnetic HgII(Stpp)Cl complex. The coordination sphere around Hg2+ in the monomeric molecule is described as a five-coordinate distorted trigonal bipyramid with the bonding to the three pyrrole nitrogens [Hg(1)–N=2.104(4), 2.626(4), 2.640(4) A], the thiophene sulfur [Hg(1)–S=2.801(1) A], and one axial chloride ligand [Hg(1)–Cl(1)=2.318(1) A]. The plane of the three pyrrole nitrogen atoms [i.e., N(1), N(2), N(3)] bonded to Hg2+ is adopted as a reference plane 3N. Because of its larger size, the Hg2+ is considerably out of the 3N plane; its displacement of 1.41 A is in the same direction as that of the apical Cl− ligand. The thiophene ring is slightly folded so that the dihedral angle between the C(13)–C(14)–C(15)–C(16) and C(13)–S(1)–C(16) planes is 7.3°.

Salicylate exchange in meso-tetraphenylporphyrinato salicylato thallium (III), Tl (tpp) (2-OH-C6H4CO2) and 13 C NMR investigation of its homolog thiocyanato (meso-tetra-p-tolyl-porphyrinato)thallium (III), Tl (tptp) (SCN)

Abstract This work determines the crystal structure of meso-tetraphenylporphyrinato salicylato thallium (III), Tl (tpp) (2-OH-C6H4CO2) (or Tl (tpp) (SA)). The coordination sphere of the Tl3 ion is an approximately square-based pyramid in which a chelating bidentate 2-OH-C6H4CO−2 group occupies the apical site. The average Tl (1)–N bond distance is 2.221 A and the Tl atom is displaced 0.76 A from the porphyrin plane. The Tl (1)–O(1) and Tl (1)–O(2) distance are 2.36 (1) and 2.47 (1) A, respectively. Variable temperature 13 C NMR measurements reveal that the salicylato group of Tl (tpp) (SA) in CD2Cl2 solvent undergoes a ligand exchange. In the slow exchange region, the carbonyl and C1″ carbons of the salicylato group are separately located at 169.6 ppm [with a 2 J (Tl–13 C) coupling constant of 157 Hz] and 111.5 ppm [with a 3 J (Tl–13 C) coupling constant of 180 Hz] for Tl (tpp) (SA) in CD2Cl2 at −90°C. In the fast exchange region, the C∗O and C1″ carbons of the 2-OH-C6H4CO−2 ligand in CD2Cl2 at 24°C are singlets at 169.8 and 112.5 ppm, respectively. The 13 C resonance of the axial isocyanato ligand in the compound thiocyanato (meso-tetra-p-tolyl-porphyrinato)thallium (III), Tl (tptp) (SCN), was observed at 110.7 ppm (24°C) with 2 J (Tl–13 C) coupling constant 253 Hz. This finding suggests that thiocyanato group is, as thiocyanate type, axially coordinated to the Tl atom in Tl (tptp) (SCN). In addition, there is no SCN − exchange in the same compound.

Crystal structures of chloro(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)Cl2, and dihydroxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OH)2, and two-stage hydrolysis of its homologue dimethoxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OMe)2

Abstract The crystal structures of chloro(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)Cl2, dimethoxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OMe)2, and dihydroxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OH)2, were determined. The coordination sphere of the Ge4+ ion is a distorted octahedron in which the apical sites are occupied by two monodentate Cl− (or OMe−, OH−) groups. The geometry around the germanium centre of the Ge(tpp)Cl2 molecule has Ge(1)Cl(1) = 2.262(1) and Ge(1)N(1) = 2.019(2) A. In the structure of Ge(tpp)(OMe)2 the germanium(1)-oxygen distance is 1.826(3), average Ge(1)N = 2.032(3), and O(1)C(23) = 1.331(6) A. The structure of Ge(tpp)(OH)2 has Ge(1)O(1) = 1.809(3) and Ge(1)N(1) = 2.027(2) A. Two-stage hydrolysis of Ge(tpp)(OMe)2 was studied by 1H and 13C NMR spectroscopy. The use of a limited amount of water in CDCl3 (or CD2Cl2) allowed the hydrolysis intermediate, hydroxomethoxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OMe) (OH), and hydrolysis product, dihydroxo(meso-tetraphenylporphyrinato)germanium(IV), Ge(tpp)(OH)2, to be identified. X-ray diffraction data and solid-state 13C CP/MAS spectra of Ge(tpp)(OMe)2 provide evidence for two monodentate methoxo groups coordinated to the germanium(IV) atom.

Thallium complexes of meso-tetra-(p-chlorophenyl)porphyrin: trifluoroacetato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) and pentafluoropropionato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III)

Abstract The crystal structures of trifluoroacetato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III), Tl[(p-Cl)4tpp](O2CCF3) (1), and pentafluoropropionato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) Tl[(p-Cl)4tpp](O2CCF2CF3) (2), were determined. The coordination sphere around the Tl3+ ion is described as five-coordinate regular square-based pyramid (RSBP) in which the apical site is occupied by an unidentate CF3CO2− ligand for 1 whereas the unidentate CF3CF2CO2− ligand occupies the axial site for 2. The plane of the four pyrrole nitrogen atoms [i.e., N(1)–N(4)] strongly bonded to Tl3+ is adopted as a reference plane 4N. The Tl3+ is moderately out of the 4N plane; its displacement of 0.58 A (or 0.59 A) for 1 (or 2) is in the same direction as that of the trifluoroacetate oxygen for 1 (or pentafluoropropionate oxygen for 2). The free energy of activation at the coalescence temperature Tc for the intermolecular trifluoroacetate exchange for 1 in CD2Cl2 is found to be ΔG≠178=36.6 kJ/mol whereas the intermolecular pentafluoropropionate exchange for 2 in CD2Cl2 is determined to be ΔG≠213=41.5 kJ/mol through 19F and 13C NMR temperature-dependent measurements.

Molecular structure of N-tosylimido-meso-tetraphenylporphyrinatozinc(II), Zn(N-NTs-tpp)

Abstract The crystal structure of N-tosylimido-meso-tetraphenylporphyrinatozinc(II), Zn(N-NTs-tpp), was determined. The zinc is tetracoordinated with the nitrogen atoms of only three pyrrole bases and with an extra nitrogen atom of the nitrene fragment. The porphyrin ring is severely distorted, the pyrrole ring bonded to the NTs ligand making a large dihedral angle of 29.1° with the plane containing the three pyrrole nitrogens bonded to the zinc (i.e. the (3N) plane) and the other pyrroles making smaller angles of 13.8, 7.6 and 5.9°. The zinc atom lies out of the (3N) plane by 0.39 A and the extra nitrogen N(4) by 1.54 A on the same side as the zinc.

Crystal structure and two-stage hydrolysis of dimethoxo (meso-tetra(4-methoxyphenylporphyrinato))tin(IV), Sn(tmpp)(OMe)2

In this work, we determine the crystal structure of dimethoxo(meso-tetra(4-methoxyphenylporphyrinato))tin(IV), Sn(tmpp)(OMe)2 (1). Experimental results indicate that the tin atom has an octahedral geometry. The geometry around the tin center has Sn(1)–O(5) = 2.020(6), Sn(1)–O(6) = 2.003(7) Å and an average Sn(1)–N = 2.10(1) Å. The two methoxo groups are unidentately coordinated to the tin(IV) atom. Two-stage hydrolysis of Sn(tmpp)(OMe)2 in CDCl3 was observed by 1H and 13C NMR spectroscopy. Compound (1) crystallizes in the space group P21/n with a = 14.7492(1), b = 19.2022(3), c = 16.0806(2) Å, β = 94.104(1)°, and Z = 4.

INTRAMOLECULAR BENZOATE EXCHANGE IN BENZOATO MESO-TETRA (4-METHOXYPHENYLPORPHYRINATO) THALLIUM(III), TL(TMPP)(C6H5CO2)

Abstract The new compound benzoato meso-tetra(4-methoxyphenylporphyrinato)thallium(III), Tl(tmpp)(C6H5CO2), has been synthesized and its molecular structure determined by X-ray analysis. The coordination sphere of the Tl3+ ion is an approximate square-based pyramid in which the apical site is occupied by an asymmetric-bidentate C6H5CO2− group. The average Tl-N bond distance is 2.24(1)A˚and the Tl atom is displaced 0.811A˚from porphyrin plane. The Tl(1)-O(5) and Tl(1)-O(6) distances are 2.57(2) and 2.27(2)A˚, respectively. Variable temperature 13C NMR measurements show that the benzoato group of Tl(tmpp)(C6H5CO2) in CD2Cl2 solvent undergoes intramolecular exchange. In the slow exchange region, the carbonyl and C1″ carbons of the benzoato group are separately located at 167.8 ppm [with 2J (Tl-13C) coupling constant 212 Hz] and 128.3 ppm [with 3J (Tl-13C) coupling constant 282 Hz] for T1 (tmpp)(C6H5CO2) in CD2Cl2 at −90°C. In the fast exchange region, the C*OO and C1″ carbons of the C6H5CO2− ligand in CD2Cl2 at 21°C are singlets at 168.4 and 130.3 ppm, respectively. The comparison of the ring current effect (Δδ) for the benzoate ligand of Tl(tmpp)(C6H5CO2) and benzoato meso-tetra(4-methoxyphenylporphyrinto)tin(IV), Sn(tmpp)(C6H5CO2)2, is also reported.

CCDC 288278: Experimental Crystal Structure Determination

Related Article: Fuh-An Yang, Kuan-Yu Cho, Jyh-Horung Chen, Shin-Shin Wang, Jo-Yu Tung, Hsi-Ying Hsieh, Feng-Ling Liao, Gene-Hsiang Lee, Lian-Pin Hwang, S.Elango|2006|Polyhedron|25|2207|doi:10.1016/j.poly.2006.01.020

Chloro(N-p-nitrobenzoylimido-meso-tetraphenylporphyrinato)iron(III): a high-spin complex

The crystal structures of diamagnetic (methanol)(N-p-nitrobenzoylimido-meso-tetraphenylporphyrinato)zinc(II) methanol solvate Zn(N-p-NCOC6H4NO2-tpp)(MeOH)·MeOH [or 4(MeOH)·MeOH] and paramagnetic chloro(N-p-nitrobenzoylimido-meso-tetraphenylporphyrinato)iron(III) Fe(N-p-NCOC6H4NO2-tpp)Cl (5), were determined. Both are pentacoordinate complexes where the p-nitrobenzoylimido (NNB) moiety is inserted into a zinc–pyrrole (or iron–pyrrole) bond. The coordination geometry of the zinc (or iron) center is best described as a distorted trigonal bipyramid with the N(2), N(5), and O(4) [or N(2), N(5), and Cl(1)] atoms lying in the equatorial plane. The plane of the three pyrrole nitrogen atoms [i.e., N(1), N(2) and N(3)] strongly bonded to Zn2+ in 4(MeOH)·MeOH (or Fe3+ in 5) is adopted as a reference plane, 3N. The porphyrin ring is severely distorted and the pyrrole ring N(4) is bonded to the NNB ligand making a dihedral angle of 30.0° (or 27.8°) with the 3N plane for 4(MeOH)·MeOH (or 5). Solid state magnetic susceptibility and the effective magnetic moment data were measured for 5 from 300 to 5 K. In the higher temperature range (T > 50 K), the effective magnetic moment is constant and is equal to 5.87 μB. This μeff value confirms that there is a high-spin ferric (S = 5/2) state for the iron atom in 5. The g values of 9.5 ± 0.4, 4.2 and 1.1 measured from X-band EPR spectra were also consistent with a high-spin ferric iron in 5. The magnitude of zero field splitting, D, and the rhombicity parameter, λ (= E/D), in 5 were determined approximately as 0.79 cm−1 and 0.29, respectively, by EPR spectroscopy and paramagnetic susceptibility measurements.