Synthesis, Structure and Characterization of the New Complex [L1(H2O)Fe(μ-O)Fe(OH2)L1]4+ [L1 =N,N′-Bis(1-methylimidazolyl-2-methyl)-N,N′-Bismethyl-1,2-ethanediamine] − Formation of the (μ-O)(μ-H3O2) Complex upon Deprotonation

A Structural and Mössbauer Study of Complexes with Fe2(μ-O(H))2 Cores: Stepwise Oxidation from FeII(μ-OH)2FeII through FeII(μ-OH)2FeIII to FeIII(μ-O)(μ-OH)FeIII

“…In contrast, the recently reported crystal structure for the related [(α-BPMEN) 2 Fe II Fe III (μ-OH) 2 ](ClO 4 ) 3 [BPMEN = N , N ‘-dimethyl- N , N ‘-bis(2-pyridylmethyl)-ethane-1,2-diamine] shows a diiron core with positional disorder so that the iron(II) and iron(III) ions could not be distinguished . The average Fe1−μ-OH and Fe2−μ-OH distances listed in Table (2.083 and 1.896 Å, respectively) for 2 correspond to those found for respective Fe−μ-OH bonds in diiron(II) 6-8 and diiron(III) complexes, − and are in very good agreement with the values for [(α-BPMEN) 2 Fe II Fe III (μ-OH) 2 ](ClO 4 ) 3 derived from EXAFS analysis . The Fe−N bond lengths, on the other hand, are rather insensitive to the iron oxidation state; the average Fe2−N bond length is shorter by only ∼0.02 Å.…”

“…Complex 3 represents a new example of a complex with the Fe III (μ-O)(μ-OH)Fe III diamond core. − The structure of this complex closely resembles that of [(BPEEN) 2 Fe 2 III (μ - O)(μ - OH)](ClO 4 ) 3 [BPEEN = N , N ‘-diethyl- N , N ‘-bis(2-pyridylmethyl)-ethane-1,2-diamine] . In particular, there is a pseudo- C 2 axis passing through the O−OH vector, relating both iron centers.…”

“…Oxo- or hydroxo-bridged non-heme diiron centers are structural motifs commonly found among proteins involved in O 2 metabolism such as hemerythrin, the hydroxylase component of methane monooxygenase (MMOH), the R2 subunit of class 1 ribonucleotide reductases (RNR R2), and fatty acid desaturases. − Efforts to model these proteins from structural and/or functional points of view have stimulated the study of complexes containing Fe(μ - O(H)) 2 Fe cores − The only example of a complex containing the Fe II (μ - OH) 2 Fe III core has very recently been described 9 and is closely related to the mixed-valence Fe II (μ - OH)(μ - OH 2 )Fe III form of MMOH. , Corresponding Fe III Fe III complexes have Fe(μ - O)(μ - OH)Fe cores owing to the Lewis acidity of the iron(III) centers; examples of such complexes have been described by us and others. − Crystallographic information for complexes containing Fe III (μ - O) 2 Fe III and Fe III (μ - O) 2 Fe IV cores is also available, ,, and a model compound containing an Fe IV (μ - O) 2 Fe IV diamond core structure has been spectroscopically characterized and the Fe IV (μ - O) 2 Fe IV diamond core structure suggested for intermediate Q in MMOH …”

The Effect of Disulphide Bond in Metallodeuteroporphyrin on Their Catalytic Activity for Aerobic Oxidation of Cyclohexane

“…In the catalytic cycle proposed for alkane oxidation by dioxygen in the presence of cytochrome P450, some stages involve the protonation or deprotonation of the sulfur residue [11]. Protonation and deprotonation of the metal-containing species are essential for hydrocarbon oxidations and often constitute the key steps of these processes [12,13]. Numerous studies have taken into account effects thiol as the axial ligands.…”