Synthese und Struktur von [Fe(SPh)₂(NO)₂]^- dem „Monomeren“ des Roussinschen Phenylesters/ Synthesis and Structure of [Fe(SPh)₂(NO)₂]^- , the “Monomer” of Roussin’s Phenyl Ester

Abstract

<jats:p>The complex (Et<jats:sub>4</jats:sub>N )[Fe(SPh)<jats:sub>2</jats:sub>(NO)<jats:sub>2</jats:sub>] (2) has been obtained as black crystals by treatment of K[Fe<jats:sub>4</jats:sub>S<jats:sub>3</jats:sub>(NO)<jats:sub>7</jats:sub>]·H<jats:sub>2</jats:sub>O with potassium hydroxide in molten diphenyldisulfide and subsequent addition of methanol and tetraethylammonium chloride. 2 is orthorhombic, space group Pbca, Z = 8, with a = 18.853(3), b = 17.958(3), and c = 13.283(2) Å at 140 K. The X-ray structure of 2 has been refined to R<jats:sub>1</jats:sub> (R2) = 2.7% (3.1% ). It reveals a pseudotetrahedral S<jats:sub>2</jats:sub>N<jats:sub>2</jats:sub> arrangement around the iron atom (Fe -S 2.280, Fe -N 1.679 Å (mean values), S -Fe -S 109.73(2)°, N -Fe -N 117.36(9)°) and Fe -N -O groups of the linear type (N -O 1.180 Å , Fe -N - O 169.0° (mean values)). The N - O bond order is 2.2. Structural properties as well as the low Mößbauer isomeric shift ( + 0.08 mm/s relative to Fe metal) are indicative of strong Fe - N π-back bonding and a major contribution of the mesomeric form Fe = N = Ō̱</jats:p><jats:p> .</jats:p>

Reactivity pathways for nitric oxide and nitrosonium with iron complexes in biologically relevant sulfur coordination spheres

“…The dark solid thus obtained was filtered and dried on a high-vacuum line for 30 min, resulting in 0.08 g (0.17 mmol, 87%) of the desired product. The spectroscopic properties are consistent with that of the known DNIC, (Et 4 N)[Fe(SPh) 2 (NO) 2 ] (4) [36,48]. Similar conditions were used to examine the reactions of (Et 4 N) 2 [Fe(SBz) 4 ] and [{Fe(S-o-NH 2 C 6 H 4 ) 2 } 2 ] with NO (g) or SNAP.…”

Heterobimetallics of Nickel−Iron Dinitrosyl: Electronic Control by Chelate and Diatomic Ligands

“…Structural and spectroscopic features are the same for 1 and [Fe(NO) 2 (SPh) 2 ] -. 15 Subsequent reaction of the [Fe(NO) 2 (SePh) 2 ]anion with dimeric [Ni(µ-SCH 2 CH 2 SCH 2 CH 2 S)] 2 in the presence of additional NO 2produced the neutral heterobimetallic [(ON)Ni-{(µ-SCH 2 CH 2 ) 2 S}Fe(NO) 2 ] complex 2, as a thermally stable, dark green-brown solid isolated in ≈70% yield. Complex 2 is soluble in hexane and THF and forms slightly air-sensitive solutions in CH 2 Cl 2 .…”

Structure of the neutral mononuclear dinitrosyl iron complex with 1,2,4-triazole-3-thione [Fe(SC2H3N3)(SC2H2N3)(NO)2]·0.5H2O

“…The first DNIC was assumed to have the anionic structure [NEt 4 ][Fe(NO) 2 (SR) 2 ] 2, where R = Ph. 3 Neutral DNIC [Fe(NO) 2 (R) 2 ] with a nitrogen-containing ligand (R = metylimidazole) was also referred to the 'g = 2.03 family', 4 though the EPR signal with g = 2.015 was only detected in solution for the [Fe(NO) 2 (R) 2 ] + form of the complex.…”