Ruthenium-Chelated Non-Innocent Bis(heterocyclo)methanides: A Mimicked β-Diketiminate.

08:00 EDT 14th August 2019 | BioPortfolio

Summary of "Ruthenium-Chelated Non-Innocent Bis(heterocyclo)methanides: A Mimicked β-Diketiminate."

The unexplored substrate-based reactivity profile of newly designed bis(heterocyclo)methanide (BHM, L1-L3), a structural mimic of ubiquitous β-diketiminate, was demonstrated on an electronically rich {Ru(acac)} platform (acac = σ-donating acetylacetonate). In this regard, this work deals with structurally characterized [Ru(L)(acac)] complexes incorporating electronically varying heterocycles {, L1 = bis(imidazo[1,5-]pyridin-3-yl)methanide; , L2 = ()-4-[(6,7-dihydrothieno[3,2-]pyridin-4-yl)methylene]-6,7-dihydro-4-thieno[3,2-]pyridin-5-ide; , L3 = ()-6-chloro-1-[(6-chloro-3,4-dihydroisoquinolin-1-yl)methylene]-3,4-dihydro-1-isoquinolin-2-ide}. The significant impact of electronic modification at the BHM backbone (L1-L3) on its redox tunability at the metal-ligand interface in and its subsequent oxygenation profile to yield bis(heterocyclo)methanone (BMO, analogue of α-ketodiimine) in the corresponding [Ru(BMO)(acac)] () via a radical pathway were rationalized. In addition, oxidative dehydrogenation of metalated BMO in to BAM [bis(heteroaryl)methanone] in [Ru(BAM))(acac)] () was illustrated in support of the nonspectator behavior of α-ketodiimine. A combined experimental and theoretical investigation extended mechanistic outlines of the aforementioned transformation processes, which in effect provided a new dimension relating to the analogous β-diketiminate as well as α-ketodiimine chemistry.


Journal Details

This article was published in the following journal.

Name: Inorganic chemistry
ISSN: 1520-510X


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Medical and Biotech [MESH] Definitions

Unstable isotopes of ruthenium that decay or disintegrate emitting radiation. Ru atoms with atomic weights 93-95, 97, 103, and 105-108 are radioactive ruthenium isotopes.

Inorganic compounds that contain ruthenium as an integral part of the molecule.

An inorganic dye used in microscopy for differential staining and as a diagnostic reagent. In research this compound is used to study changes in cytoplasmic concentrations of calcium. Ruthenium red inhibits calcium transport through membrane channels.

Complex of iron atoms chelated with carbonyl ions.

A hard, brittle, grayish-white rare earth metal with an atomic symbol Ru, atomic number 44, and atomic weight 101.07. It is used as a catalyst and hardener for PLATINUM and PALLADIUM.

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