Modeling Hydrolysis at Dinuclear Iron Centers

Nitrate‐ and Nitrite‐Assisted Conversion of an Acetonitrile Ligand Into an Amidato Bridge at an {Mo2(Cp)2(μ‐SMe)3} Core: Electrochemistry of the Amidato Complex [Mo2(Cp)2(μ‐SMe)3{μ‐η1,η1‐OC(Me)NH}]+

“…[18,22] However, in these compounds trast to what is observed here: addition of a large excess of acetonitrile has no effect on the CV shown in Figure 3a. Therefore, it is unlikely that the species observed in THF in the presence of perchlorate arises from the simple substitution of ClO 4 -as compared to acetonitrile.…”

“…It is thought that the metal centres in these enzymes act cooperatively, the role of one of them being to modify the pK a of a bound water molecule, thus generating a hydroxide ligand that attacks the substrate present at the neighbouring metal centre. [17,18] Similar reactions can involve mononuclear complexes. The metal-promoted hydrolysis of a nitrile ligand in the side chain of a tetrazamacrocyclic Cu complex has been reported recently.…”

“…Therefore, it appears that the reactivity (the lability) of the acetonitrile bound to one Mo atom is affected by the nature of the ligand present at the adjacent metal centre of the {Mo 2 -(Cp) 2 (µ-SMe) 3 } site. Several compounds containing an amidato ligand are known, [17,18,25] although no electrochemical study of such a complex has been reported so far, to the best of our knowledge. We now report the electrochemistry of 2 0/+ in THF and MeCN containing [NBu 4 ][PF 6 ].…”

A dinuclear oxo-bridged Fe(III) complex with tris(2-pyridylmethyl) amine: Structure and Hirshfeld surface analysis

“…Analysis of intermolecular interactions using Hirshfeld surface-based tools represents a major advance in enabling supramolecular chemist to gain insight into crystal packing behavior. A search of the Cambridge Structural Database [59] with Fe(III)TPA yielded 52 hits (excluding duplicate structure determinations), 46 of which had different coordination geometry, with the remaining 6 containing similar coordination geometry (GUCHIV [60], KEYXOC [61], POJCOG [62], TINRIS [63], UFOJUV [64] and WIHSAH [47]), where the TPA ligand coordinates the Fe(III) atom in the similar fashion. The identification of characteristic interactions to the Hirshfeld surface throughout these structures is however, yet to be reported.…”

Potential-modulated DNA Cleavage by (N-Salicylideneglycinato)-copper(II) Complex

“…For this reason, the studies of the reactivity of these complexes were performed in a nonaqueous solvent such as acetonitrile. 20,21 If these complexes were to be used as antitumor therapies, it was imperative to find that these complexes were soluble and to establish a new method where DNA cleavage can be performed under physiological conditions.…”