(2,3,7,8,12,13,17,18-Octa­ethyl­por­phin­ato)(trifluoro­methane­sulfonato)iron(III)

The title compound, [Fe(CF3O3S)(C36H44N4)], is an iron(III) porphyrin complex with the trifluoro­methane­sulfonate anion as an axial ligand. The Fe atom is displaced by 0.219 (2) Å toward the trifluoro­methane­sulfonate anion from the 24-atom mean plane of the porphyrin, resulting in a distorted FeN4O square-based pyramidal geometry. One ethyl­ene group is disordered over two orientations in a 0.502 (6):0.498 (6) ratio

[5,10,15,20-Tetra­kis(4-meth­oxy­phen­yl)porphyrinato-κ4 N,N′,N′′,N′′′](trifluoro­methane­sulfonato-κO)­iron(III)

The title compound, [Fe(CF3O3S)(C48H36N4O4)], is a five-coordinate iron(III) porphyrin complex with a trifluoro­methane­sulfonate anion as an axial ligand. The FeIII atom is displaced by 0.40 (1) Å towards the trifluoro­methane­sulfonate anion from the 24-atom mean plane of the porphyrin. The average Fe—Np distance is 2.044 (2) Å and the Fe—O distance is 2.001 (2) Å

Dinitro­sylbis[tris­(4-chloro­phen­yl)phosphane]iron

The title dinitrosyl iron diphosphane complex, [Fe(NO)2(C18H12Cl3P)2] or Fe(NO)2 L 2 [L = P(C6H4-p-Cl)3] belongs to the family of metal dinitrosyl compounds with the general formula Fe(NO)2(L)x, referred to collectively as dinitrosyl iron compounds (DNICs). The iron atom is tetra­hedrally coordinated by two phosphane ligands and two NO groups with Fe—N—O bond angles of 178.76 (15) and 177.67 (14)°

Chloridonitros­yl[meso-5,10,15,20-tetra­kis­(p-tol­yl)porphyrinato-κ4 N,N′,N′′,N′′′]osmium(II) tetra­hydro­furan tetra­solvate

The title compound, [OsCl(NO)(C48H36N4)]·4C4H8O, is a six-coordinate osmium(II) porphyrin complex with nitrosyl (NO) and chloride (Cl) ligands trans to each other in an octa­hedral geometry. The metal complex lies on a fourfold rotation axis that passes through the Os, N, O and Cl atoms. The NO and Cl ligands are disordered in an 0.511 (12):0.486 (12) ratio

(Ethanolato)[2,3,7,8,12,13,17,18-octa­ethylporphyrinato(2−)]iron(III)

The title compound, [Fe(C2H5O)(C36H44N4)], contains a five-coordinate iron–porphyrin complex with an axial eth­oxy ligand. The iron(III) atom is displaced by 0.504 (2) Å towards the eth­oxy ligand from the 24-atom mean plane of the porphyrin. The average Fe—Np distance is 2.078 (2) Å and the Fe—O distance is 1.8232 (18) Å. The eth­oxy C atoms are disordered in a 0.581 (12):0.419 (12) ratio. The bond angles of the Fe—O—C linkage are 128.6 (3) and 130.4 (3)°, respectively, for the major and minor occupancy C atoms

Preparation, Characterization, Electrochemistry, and Infrared Spectroelectrochemistry of Ruthenium Nitrosyl Porphyrins Containing η1-O Bonded Axial Carboxylates

The synthesis, characterization and redox behavior of eight low-spin nitrosyl carboxylate compounds (por)Ru(NO)(η1-OC(=O)R) (por = T(p-OMe)PP: R = Me (1), i-Pr (2), t-Bu (3), p-C6H4NO2 (4), Fc (5), CF3 (8); por = TTP: R = Fc (6)) and (T(p-OMe)PP)Ru(NO)(OC6HF4) (7) are reported. The compounds are moderately stable in air as solids. Their IR (KBr) spectral data show ʋNO\u27s in the 1839-1861 range cm-1. The X-ray crystal structures of compounds 1, 2, 5-7, and 8 have been determined, and reveal linear RuNO linkages for these formally {RuNO}6 complexes. The redox behavior of the compounds at a Pt working electrode were studied in CH2Cl2 with NBu4PF6 as supporting electrolyte. The compounds display reversible first oxidations. IR spectroelectrochemistry of compounds 1-4, 7 and 8 revealed porphyrin centered oxidations, whereas the ferrocenylcarboxylate compounds revealed first oxidations at the ferrocenyl moiety followed by second oxidations at the porphyrin macrocycles. Reductions of these compounds are accompanied by loss of the axial ligands

Dinitro­sylbis[tris­(4-methyl­phen­yl)phosphane]iron

The title compound, [Fe(NO)2(C21H21P)2], belongs to the family of metal dinitrosyl compounds with the general formula Fe(NO)2(L)x, referred to collectively as ‘dinitrosyl iron compounds’ (DNICs). Herein we report the structure of a dinitrosyl iron diphosphane complex, [Fe(NO)2 L 2], with L = P(C6H4-p-CH3)3. There are two crystallographically independent but chemically equal mol­ecules per asymmetric unit. The iron atom in each mol­ecule is tetra­hedrally coordinated by two phosphane ligands and two NO groups, with Fe—N—O angles in the range 173.84 (15)–179.31 (16)°

Electrochemical investigation of the kinetics of chloride substitution upon reduction of [Ru(porphyrin)(NO)Cl] complexes in THF.

The electrochemistry of several ruthenium porphyrin nitrosyl chloride complexes [Ru(por)(NO)Cl] have been examined in tetrahydrofuran. The complexes undergo 1-electron irreversible reductions which result in the diffusion-limited substitutions of the chloride ligands for THF. This chloride metathesis is reversible in the presence of added NBu4Cl, and equilibrium constants and rate constants for chloride loss have been estimated. These parameters correlate with the NO stretching frequencies of the parent complexes, with more electron-donating porphyrin ligands favouring chloride loss from the reduced complexes. The [Ru(por)(NO)(THF)] products of the reductions can be detected by IR, EPR and visible spectroscopies. These species undergo three further reductions, with good reversibility at scan rates \u3e0.40 V s-1. The [Ru(por)(NO)(THF)]+/0 couples have also been determined, and the rate constants and equilibrium constants for recombination with chloride have been estimated. One-electron reductions of the [Ru(por)(NO)Cl] complexes result in ~1018 enhancement of the rates of chloride loss

(Nitrato-κO)oxido(5,10,15,20-tetra­phenyl­porphyrinato-κ4 N)molybdenum(V) benzene solvate

In the title compound, [Mo(C44H28N4)(NO3)O]·C6H6, the porphyrin ring is centrosymmetric. The Mo atom, oxide ion and nitrate ion are equally disordered over two sites, such that the Mo atom is displaced by 0.366 (1) Å towards the oxide ion from the 24-atom mean plane of the porphyrin, and also makes a long Mo—O bond to a nitrate O atom. A centrosymmetric benzene solvent mol­ecule is situated between adjacent porphyrin mol­ecules