Jo-Yu Tung

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°.

A 13C and 1H NMR spectroscopic investigation of the structure of the iminium ion with a dipolar form in metal complexes of 2-N-substituted N-confused porphyrins

The crystal structures of chloro(2-aza-2-ethoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) zinc(II) [Zn(2-NCH2COOC2H5NCTPP)Cl; 4], (2-aza-2-ethoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) palladium(II) [Pd(2-NCH2COOC2H5NCTPP); 5], bromo(2-aza-2-ethoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) manganese(III) [Mn(2-NCH2COOC2H5NCTPP)Br; 6], [2-aza-(3′-phenoxypropyl)-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′] nickel(II) [Ni(2-NCH2CH2CH2OC6H5NCTPP); 7] and chloro(2-aza-2-methoxycarbonylmethyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N′N′′) zinc(II) [Zn(2-NCH2COOCH3NCTPP)Cl; 8] have been established. The g value of 9.54, which was measured from the parallel polarization of the X-band EPR spectra in CHCl3 at 4 K, is consistent with the high spin mononuclear manganese(III) centre (S = 2) in 6. The magnitude of the axial (D) zero-field splitting (ZFS) for the mononuclear Mn(III) centre in 6 was determined approximately to be 1.63 cm(−1) by paramagnetic susceptibility measurements. The NMR spectroscopic investigation of the iminium ion with a dipolar canonical contribution to the metal complexes 5–7, Pd(2-NCH2C6H5NCTPP) (10) and Ni(2-NCH2C6H5NCTPP) (11) in CDCl3 is reported. A resonance between the dipolar canonical form II and covalent canonical form I exists for complexes 5–7, 10 and 11 in CDCl3. To develop the correlations between δ13C [C(3)], δ1H [H(3)] and the canonical form II in 5–7, 10 and 11, this work thoroughly examines the 13C and 1H NMR of N+=CH(Ar) fragment on seven metal complexes of 2-N substituted N-confused porphyrin. According to these results, the 13C [C(3)] and 1H [H(3)] chemical shifts of the N+=CH(Ar) fragment at 20 °C in CDCl3 are separately located at 152.6 ± 0.5 and 8.30 ± 0.15 ppm respectively for the iminium ion. This exists as a dipolar canonical form II for complexes 5–7, 10 and 11, and the N–CH(Ar) group appears at 121.1 ± 0.1 ppm and 6.35 ± 0.01 ppm, which is in a covalent canonical form I contribution to complexes 4 and 8. X-Ray diffraction data indicate that N(2)–C(3) = 1.315 ± 0.011 Å for the dipolar contribution of 5–7, 10–13, while N(2)–C(3) = 1.331 ± 0.008 Å for the covalent contribution of 4 and 8.

Unusual Inner C‑Alkylation of 2‑N-Substituted N‑Confused Porphyrin Cobalt Complexes in Toluene and p‑Xylene

The inner C-benzyl- and C-p-xylyl-substituted cobalt(II) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NCH2COOCH2C6H5NCTPPH (1) and CoCl2·6H2O in toluene (or p-xylene), and the structures were revealed by single-crystal X-ray analysis.

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.

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.

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