[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

(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

Dinitro­sylbis[tris­(4-fluoro­phen­yl)phosphane]iron chloro­form monosolvate

The title compound, [Fe(NO)2(C18H12F3P)2]·CHCl3, 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-F)3. The structure includes one metal complex mol­ecule and one chloro­form solvent mol­ecule. The iron atom is tetra­hedrally coordinated with two phosphane ligands and with two NO groups with Fe—N—O angles of 178.1 (2) and 177.0 (2)°

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

Over or Under: Hydride Attack at the Metal versus the Coordinated Nitrosyl Ligand in Ferric Nitrosyl Porphyrins.

Hydride attack at a ferric heme–NO to give an Fe–HNO intermediate is a key step in the global N--‐cycle. We demonstrate differential reactivity when six--‐ and five--‐coordinate ferric heme--‐NO models react with hydride. Although Fe–HNO formation is thermodynamically favored from this reaction, Fe–H formation is kinetically favored for the 5C case

Bis[1,3-bis­(2,4,6-trimethyl­phen­yl)-2,3-dihydro-1H-imidazol-2-yl­idene]dichloridodinitro­syltungsten(II) tetra­hydro­furan-d 8 monosolvate

The mol­ecular structure of the title compound, [WCl2(NO)2(C21H24N2)2]·C4D8O, displays a distorted octa­hedral arrangement around the W atom with two trans 1,3-bis­(2,4,6-trimethyl­phen­yl)imidazol-2-yl­idene (IMes) carbene ligands in axial positions. The four equatorial positions are occupied by nitrosyl and chloride ligands, which are trans to each other. The Ccarbene—W—Ccarbene bond angle of 173.44 (18)° and the Cl—W—Nnitros­yl bond angles of 171.34 (11) and 171.32 (13)° deviate only slightly from linearity. The distortion comes from the nitrosyl and chloride ligands which are not fully coplanar since the two N atoms deviate from the WCl2 plane by −0.279 (4) and 0.272 (4) Å, respectively. An inter­molecular C—H⋯O inter­action connects the organometallic mol­ecule and the tetra­hydro­furan-d 8 solvent mol­ecule

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)°