The design of multianionic chelating ligands for the production of inorganic oxidizing agents. Osmium coordination chemistry that provides stable potent oxidizing agents and stable potent reducing agents

Analysis of Hydrogen Atom Abstraction from Ethylbenzene by an FeVO(TAML) Complex

“…To elucidate the role of high-valent iron–oxo species, chemists have designed biomimetic model complexes capable of activating C–H bonds, including Fe IV species ,− and Fe V species, − the latter supported by tetraamido macrocyclic ligands (TAML, Figure ). − With molecular weights around 500 Da, i.e., at only less than 1% the size of oxygen and peroxide activating enzymes, iron–TAML activators are functional mimics of the peroxidase and short-circuited cytochrome P450 enzymes. , TAML systems support multiple Fe IV − and the first spectroscopically characterized Fe V O complex . This Fe V O TAML species is demonstrably more reactive than Fe IV TAML complexes. , …”

Designing Ligands for Oxidizing Complexes

“…These ligand degradations appear to be best formulated as two-electron processes, and eq 1 shows what happens to the sensitive portion of one of the ligands. 19,30 Here it is useful to introduce a concept to emphasize the possible presence of communication channels comprised of overlapping orbitals between the metal ion and remote ligand sites that establish favorable conditions for oxidative ligand degradations. The reaction of eq 1 can be conceptualized as a remote reductive elimination, in this case a 1,3-reductive elimination (1,3-RE), with the /3-carbon atom in the 1-position and the metal atom in the 3-position.…”

Synthesis of a new family of water-soluble clusters: Ru3(CO)12-xLx (x = 1-3), Os3(CO)10L2, and Ir4(CO)9L3 (L = trisodium salt (hydrated) of tris(m-sulfonatophenyl)phosphine)

“…I3 An ORTEP diagram of the molecular structure of 2a is shown in Figure 1 . The Os(6)-C( 17) distance of 2.05 (2) A is similar to the osmiumcarbon (carbene) distances of 2.026 (15) 8, [2.04 (2) An ORTEP diagram of the molecular structure of 2b is shown in Figure 2.Is The molecule contains a cluster of six osmium atoms. Each triangle is bridged by a sulfido ligand.…”