The η-H-CHg agostic interactions in the mercury complexes of N-confused porphyrin.

Six four-coordinated complexes of the chemical formulae [Hg(2-N CH2COOCH2CH3-21-H-NCTPP)X] with X = Cl (5), Br (6), I (7), [Hg(2-NCH3-21-H-NCTPP)Cl] (4) and [Hg(2-NCH2COOCH2C6H5-21-H-NCTPP)X] with X = Cl (8), I (9) are synthesized and structurally determined. The bond path for the weak η1-H(17)-C(17)Hg agostic interactions between the Hg center and H(17) in complexes 4-9 was a through-space interaction from Hg to agostic carbon [C(17)] followed by a through-bond interaction from C(17) to an agostic proton [H(17)]. The magnitude of J[Hg-H(17)] [or the agostic upfield shift Δδago of the C(17)] for these complexes increases as the halide ligand varies from iodide to chloride, ranging from 33.

Axial zero-field splitting in mononuclear Co(ii) 2-N substituted N-confused porphyrin: Co(2-NC3H5-21-Y-CH2C6H4CH3-NCTPP)Cl (Y = o, m, p) and Co(2-NC3H5-21-CH2C6H5-NCTPP)Cl.

The inner C-benzyl- and C-o-xylyl (or m-xylyl, p-xylyl)-substituted cobalt(ii) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NC3H5NCTPPH (1) and CoCl2·6H2O in toluene (or o-xylene, m-xylene, p-xylene). The crystal structures of diamagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-hydrogen-21-carbaporphyrinato-N,N',N'')zinc(ii) [Zn(2-NC3H5-21-H-NCTPP)Cl; 3 ] and paramagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-benzyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-CH2C6H5NCTPP)Cl; 7], and chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-Y-xylyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-Y-CH2C6H4CH3NCTPP)Cl] [Y = o (8), m (9), p (10)] were determined. The coordination sphere around the Zn(2+) (or Co(2+)) ion in 3 (or 7-10) is a distorted tetrahedron (DT).

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.

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.

Intermediate (S = 1) spin state in five-coordinate cobalt(III): magnetic properties of N-o-hydroxy-benzamido-meso-tetraphenylporphyrin cobalt(III), Co(N-NCO(o-O)C6H4-tpp).

The crystal structures of paramagnetic N-o-oxido-benzimido-meso-tetraphenylporphyrinato (-kappa(4),N(1),N(2),N(3),N(5),kappaO(2))cobalt(III) [Co(N-NCO(o-O)C(6)H(4)-tpp); 2] (S = 1) and diamagnetic N-o-oxido-benzimido-meso-tetraphenylporphyrinato (-kappa(4),N(1),N(2),N(3),N(5),kappaO(2)) gallium(III) chloroform.methanol solvate [Ga(N-NCO(o-O)C(6)H(4)-tpp).0.

Magnetic susceptibility and ground-state zero-field splitting in high-spin mononuclear manganese(III) of inverted N-methylated porphyrin complexes: Mn(2-NCH3NCTPP)Br.

The crystal structures of diamagnetic dichloro(2-aza-2-methyl-5,10,15,20-tetraphenyl-21-carbaporphyrinato-N,N',N'')-tin(IV) methanol solvate [Sn(2-NCH 3NCTPP)Cl 2.2(0.2MeOH); 6.

ESR, zero-field splitting, and magnetic exchange of exchange-coupled copper(II)-copper(II) pairs in copper(II) tetraphenylporphyrin N-oxide.

The crystal structures of the dimer form of copper(II) tetraphenylporphyrin N-oxide, [Cu(tpp-N-O)]2 (3-dimer), and zinc(II) tetraphenylporphyrin N-oxide, [Zn(tpp-N-O)]2 (4-dimer), were established. The geometry at the copper ion in 3-dimer is essentially square-pyramidal with one oxygen bridge [O(1A)] occupying the apical site, giving a much larger Cu-O bond distance compared to those at the basal plane. The respective Cu.