Pyridine- and phosphine-based ligands modified with ethacrynic acid (a broad acting glutathione transferase inhibitor) were prepared and coordinated to ruthenium(II)-arene complexes and to a ruthenium(III) NAMI-A type complex. All the compounds (ligands and complexes) were fully characterized by analytical and spectroscopic methods and, in one case, by single-crystal X-ray diffraction. The in vitro anticancer activity of the compounds was studied, with the compounds displaying moderate cytotoxicity toward the human ovarian cancer cell lines. All the complexes led to similar levels of residual GST activity in the different cell lines, irrespective of the stability of the Ru-ligand bond.

A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and nontoxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups -monophosphines, bisphosphines and miscellaneous -was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts.

Formation of carbocations from phenyl-acetic acids is mediated by W(vi) chloride and takes place at room temperature with the extrusion of carbon monoxide.

The full potential of a high valent metal chloride as both a chlorinating and an oxidative agent was explored by allowing WCl to react with N-(2,6-diisopropylphenyl) α-diimines, in CHCl at room temperature. These α-diimines underwent unprecedented conversion to quinoxalinium cations via intramolecular C-N coupling.

We recently reported a density functional theory (DFT) analysis of the Nb­(V)–C bond in various NbCl5(L) complexes, discovering that the carbon ligand L receives electronic density from the metal (classical back-donation) and from the chlorides in the cis position (direct interligand interaction). Here we report the synthesis and the structural characterization of two new coordination compounds of niobium pentahalides, i.e., NbX5(CNXyl) (X = Cl, Br; Xyl = 2,6-C6H3Me2), and the corresponding DFT analyses of the Nb­(V)–C bond using the Natural Orbitals for Chemical Valence-Charge Displacement (NOCV-CD) approach, confirming the presence of a cis-halide → isocyanide direct interligand interaction. To verify whether the latter is limited to Nb complexes or not, we performed a NOCV-CD analysis on a series of several organometallic complexes based on Ti­(IV), Nb­(V), Ta­(V), Rh­(III), Pd­(II), and Au­(III), all of which bear one halide ligand and m-xylyl-isocyanide in a mutual cis position, revealing that the cis-halide → isocyanide interaction is always present.

A mild, oxidative fluorination approach to a variety of fluorinated phosphorus compounds using trichloroisocyanuric acid (TCICA) and KF was developed as a complement to a recent study on deoxygenative fluorination using oxalyl chloride. Herein, the syntheses of several fluorinated organophosphorus compounds are reported, and both TCICA/KF and oxalyl chloride/KF conditions are compared and contrasted throughout. Initial investigations of the method on other group 15 heteroatoms (i. e., As, Sb, and Bi) are also reported, with varied success. This work notably extends the known TCICA/KF reactivity series to another group of elements beyond previously studied chalcogens (S, Se, and Te) and halogens (iodine) and expands the utility of the previously reported oxalyl chloride/KF method.

The 1-:-1 molar reactions at room temperature of MoCl5 with aliphatic amines were investigated in dichloromethane. Pyrrolidine, diethylamine and dibenzylamine underwent dehydrogenative oxidation when allowed to react with MoCl5; the compounds [MoCl5NCH(CH2)3], 1, and [CH3CHNHEt][MoOCl4], 2, were isolated in moderate to low yields from MoCl5/pyrrolidine and MoCl5/NHEt2, respectively. The chloride-amide complex [MoCl4(NEt2)], 3, was afforded in 65% yield from MoCl5 and Et2NSiMe3. The interaction of MoCl5 with Me2NSiMe3 was accompanied by activation of the solvent, and the complexes [MoCl3(NMe2)(κ2-Me2NCH2NMe2)], 4a, and [MoCl3(NMe)(κ2-Me2NCH2NMe2)], 4b, co-crystallized from the reaction mixture. The reactions of MoCl5 with a series of primary amines afforded mixtures of products, and the Mo(vi) chloride imido complexes [MoCl4(NR)]2 (R = Cy, 5a; tBu, 5b) were isolated in ca. 40% yield from MoCl5/NH2R (R = Cy, tBu). C-H bond activation may be viable in the reactions of MoCl5 with tertiary amines: the compounds [(CH2Ph)2NCHPh]2[MoCl6]·CH2Cl2, 6, and [NHEt3]2[Mo2Cl10], 7, were obtained from MoCl5/tribenzylamine and MoCl5/triethylamine, respectively. Pyrrolidine and tribenzylamine underwent analogous activation pathways when allowed to react with [MoCl3OCH(CF3)2]2 in the place of MoCl5. The isolated metal products were characterized by analytical and spectroscopic techniques, in addition the structures of 1, 2, 4, 5a, 6·CH2Cl2 and 7 were ascertained by single crystal X-ray diffraction studies. The organic products were identified by NMR and GC-MS after hydrolysis of the reaction mixtures. DFT calculations were carried out in order to assist the IR assignments, and clarify structural and mechanistic aspects

The direct interactions of WCl6and MoCl5with α-diimines (and also a carbodiimide in the case of MoCl5) have been explored, leading to unusual reaction pathways.