An oxo(corrolato)chromium(V) complex selectively kills cancer cells by inducing DNA damage.

An oxo(corrolato)chromium(v) complex selectively kills leukemia cells. However, this complex did not induce cell death in primary non-cancer cells. It has been observed that oxo(corrolato)chromium(v) complex induced cell death is associated with DNA damage. Interestingly, the DNA in primary cells largely remained unaffected. DNA isolated from normal and cancerous cell lines also follows similar trends. A chemical reductant, DTT, was used to probe the mechanism of DNA damage. However, it does not show any additive effect on DNA damage.

A new synthesis of porphyrins via a putative trans-manganese(iv)-dihydroxide intermediate.

A new method for the synthesis of meso-substituted porphyrins was developed. In this two-step methodology, the first step involves the condensation of pyrroles/dipyrromethanes with aldehydes in a water-methanol mixture under acidic conditions. The second step involves manganese induced cyclization followed by oxidation via PhIO/O2. This methodology has been useful for the synthesis of a wide range of trans-A2B2 porphyrins and also symmetric porphyrins in moderate to good yields. A detailed investigation of the manganese induced cyclization reaction has allowed us to characterize a Mn-porphyrinogen complex. A series of analytical and spectroscopic techniques and DFT calculations have led us to the conclusion that the putative intermediate species are trans-manganese(iv)-dihydroxide complexes. EPR and magnetic susceptibility measurements helped us to assign the oxidation state of the manganese complexes in their native state. The assumption of trans-manganese(iv)-dihydroxide as the true intermediate for this porphyrin synthesis has been authenticated via in situ UV-Vis experiments. This new methodology is certainly different from other previously reported methodologies in many aspects and most importantly these reactions can be easily performed on a gram scale for the synthesis of porphyrins.

Regioselective thiocyanation of corroles and the synthesis of gold nanoparticle-corrole assemblies.

Herein we demonstrate a synthetic protocol for the regioselective thiocyanation of corroles. To the best of our knowledge, thiocyanato appended corrole has never been reported earlier. The resulting thiocyanato appended corrole turned out to be a good corrole based precursor for the facile synthesis of thiol protected gold nanoparticles (Au NPs). The ligand system acts as a good bidentate framework and passivates the gold surface. A strong electronic interaction between the corrole and the gold nanoparticles is manifested by their unique photo physical properties and it also confirms that the binding through ß-substitutions has a more pronounced effect even though the corrole rings are face-off to the gold surface.

Metal coordination induced ring contraction of porphyrin derivatives.

A remarkable rearrangement of a diferrocenylporphyrin to give a silver(iii) corrole has been discovered. Compared to the previously reported porphyrin to corrole ring conversions (extremely rare and poor reaction yields), our methodology delivers near quantitative yield for this ring contraction.

Isovalent AgIII /AgIII , AgII /AgII , Mixed-Valent AgII /AgIII , and Corrolato-Based Mixed-Valency in ß,ß'-Linked [Bis{corrolato-silver}]n Complexes.

Mixed-valent compounds are fascinating entities that are useful as models for investigating electron-transfer reactions, and find use in a host of biologically relevant redox processes. Though the bio-relevant metal copper is well established in mixed-valent chemistry, the AgII /AgIII mixed-valent combination of its higher congener in a molecular complex has rarely been reported before. This work reports the synthesis of a new ß,ß'-linked bis{corrolato-silver(III)} complex and its characterization in five different redox states. A combination of electrochemistry, spectroelectrochemistry, and DFT calculations point to the existence of a mixed-valent AgII /AgIII and an isovalent AgII /AgII form. Additionally, characterization of the AgIII /AgIII form and ligand-based corrolato-centered mixed-valency is presented as well. These results thus open new avenues for bis-corrolato ligands and for mixed-valency in disilver compounds.

Ruthenium-Ruthenium-Bonded [Bis{corrolato-ruthenium(III)}]n (n=0, +1, -1) Complexes: Model Compounds for the Photosynthetic Special Pair.

We present herein the synthesis of three new bis(corrolato-ruthenium(III)) complexes containing unsupported Ru-Ru bonds and their characterization in different redox states. The 1 H NMR spectra of the bis(corrolato-ruthenium(III)) complexes displayed "normal" chemical shifts and the compounds proved to be EPR-silent. Crystallographic characterization of the dimers indicated Ru-Ru distances of 2.175 Å, consistent with a triple bond between the two ruthenium centers. All of the synthesized complexes undergo two successive reversible oxidations and a single reversible reduction. A combination of UV/Vis/NIR/EPR spectroelectrochemical studies and DFT calculations established the redox state distributions in these ruthenium-ruthenium-bonded dimers. Whereas reduction of the dimers is metal-based and leads to metal-metal-bonded mixed-valent RuII -RuIII species, one-electron oxidation largely retains the RuIII -RuIII situation with the generation of metal-bound corrolato radicals. The present study thus concerns the first UV/Vis/NIR/EPR spectroelectrochemical characterization and DFT calculations of ruthenium-ruthenium-bonded rotationally ordered corrole dimers. The mean plane separation between the two corrole units in these dimers is around 3.543 Å, which is in close agreement to that in the "special pair" in chlorophyll. Oxidation of these ruthenium-ruthenium-bonded dimers gives rise to two new electronic absorption bands in the NIR region (similar to those of the special pair), which have apparently not been mentioned/observed in earlier reports on ruthenium-ruthenium-bonded corrole dimers. These bands mainly originate from inter-corrole transitions.