The diiminepyridine ligand, made famous by Brookhart and Gibson a decade ago through its use in the first iron-containing olefin polymerization catalyst, also displays an amazing variety of ligand-centred reactions, including electron transfer, alkylation, dimerization and deprotonation. The present Perspective summarizes these reactions and also speculates on the links between ligand- and metal-centred reactivity.
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http://dx.doi.org/10.1039/b612251e | DOI Listing |
Dalton Trans
May 2022
Laboratory for Zero-Carbon Energy, Institute of Innovative Research, Tokyo Institute of Technology 2-12-1 N1-32, O-okayama, Meguro-ku, 152-8550 Tokyo, Japan.
A uranyl(VI) complex with 2,6-bis(3,5-di--butyl--phenolateaminomethyl)pyridine (UO(Bu-pdaop), 1) was synthesized and thoroughly characterized by H NMR, IR, elemental analysis, and single-crystal XRD. Right after the dissolution of complex 1 in pyridine or DMSO, the solution was pale red, whereas it gradually turned to dark purple under an ambient atmosphere. H NMR spectra at the initial and final states suggested that both of the two aminomethyl groups in 1 were converted to azomethine ones through aerobic oxidation.
View Article and Find Full Text PDFChem Sci
May 2020
Department of Chemistry, University of Warwick Coventry CV4 7AL UK
Organometallic complexes with novel activation mechanisms are attractive anticancer drug candidates. Here, we show that half-sandwich iodido cyclopentadienyl iridium(iii) azopyridine complexes exhibit potent antiproliferative activity towards cancer cells, in most cases more potent than cisplatin. Despite their inertness towards aquation, these iodido complexes can undergo redox activation by attack of the abundant intracellular tripeptide glutathione (GSH) on the chelated azopyridine ligand to generate paramagnetic intermediates, and hydroxyl radicals, together with thiolate-bridged dinuclear iridium complexes, and liberate reduced hydrazopyridine ligand.
View Article and Find Full Text PDFDalton Trans
October 2020
Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
Reactions of B(C6F5)3 with the β-diketiminato (BDI) alkaline-earth phosphidoborane complexes, 1a [(BDI)Ca(H3B·PPh2)] and 1b [(BDI)Mg(H3B·PPh2)]2 (BDI = [HC{C(CH3)N(2,6-iPr-C6H3)}2]-) result in the formation of phosphinodiboronate complexes 4a [(BDI)Ca(η6-toluene){H3B·PPh2·B(C6F5)3}] and 4b [(BDI)Mg{H3B·PPh2·B(C6F5)3}]. Calcium complex 4a is stable in aromatic solvents at room temperature and does not display well-defined onward reactivity at elevated temperatures. Magnesium complex 4b undergoes a room temperature transformation to provide the known hydridoborate derivative 3b [(BDI)Mg{HB(C6F5)3}] and an N,P,N'-ligated species, 5 [{HC(C(CH3)N(2,6-iPr-C6H3))2(H2BPPh2)}Mg{H3B·PPh2·B(C6F5)3}] that results from interception of the putative phosphinoborane, H2B = PPh2, by the BDI ligand backbone following B(C6F5)3-mediated hydride abstraction.
View Article and Find Full Text PDFDalton Trans
September 2019
Department of Chemistry, Gauhati University, Guwahati 781014, Assam, India.
Herein, two ternary cobalt(ii) complexes, namely [Co(9-accm)(phen)](OAc) (1) and [Co(9-accm)(dppz)](OAc) (2), where 9-accmH is 1,7-(di-9-anthracene-1,6-heptadiene-3,5-dione), phen is 1,10-phenanthroline and dppz is dipyrido[3,2-a:2',3'-c]phenazine, having an anthracene-based curcuminoid and phenanthroline bases were synthesized and fully characterized, and their in vitro photocytotoxicities were studied in cancer cells. To understand the role of the curcuminoid ligand 9-accm in photo-activated cytotoxicity, two control complexes, viz. [Co(dbm)(phen)](OAc) (3) and [Co(dbm)(dppz)](OAc) (4), where dbmH is 1,3-diphenyl-1,3-propanedione (dibenzoylmethane), were prepared and used for the control experiments.
View Article and Find Full Text PDFChem Commun (Camb)
October 2014
Department of Chemistry, University of Victoria, PO Box 3065 STN CSC, Victoria, BC V8W 3V6, Canada.
Reactivity studies of a Pd(II)-verdazyl complex reveal novel ligand-centred reduction processes which trigger pseudo-reductive elimination at Pd. Reaction of the complex with water induces a ligand-centred redox disproportionation. The reduced verdazyl ligands can also be reversibly protonated.
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