Phenoxazinyl Zn(II) diradical complex formed via redox-driven cyclization of a 2-aminophenol-based N3O ligand. Isolation of the modified N3 ligand radical and its Ni(II) complex.

Aerobic reaction between the pyridine-2-carboxamide-2-aminophenol N3O ligand (H3L1) and Zn(ClO4)2·6H2O in CH3CN affords an N3 phenoxazinylate coordinated Zn(II) complex; its diradical electronic structure [ZnII{(L1*)˙-}2] has been elucidated from redox, spectroscopic (UV-VIS and EPR), and magnetic measurements and DFT calculations. Isolation and characterization of the metal-assisted redox-driven modified N3 ligand as a radical cation (H2L1*)˙+ and its Ni(II)-diradical complex [NiII{(L1*)˙-}2] have also been achieved.

Carbonylative Transformations Using a DMAP-Based Pd-Catalyst through Ex Situ CO Generation.

A phosphine-free, efficient protocol for aminocarbonylation and carbonylative Suzuki-Miyaura coupling has been developed using a novel palladium complex, [PdII(DMAP)2(OAc)2]. The complex was successfully synthesized using a stoichiometric reaction between PdII(OAc)2 and DMAP in acetone at room temperature and characterized using single-crystal X-ray analysis. Only 5 mol % catalyst loading was sufficient for effective carbonylative transformations. "Chloroform-COware" chemistry was utilized for safe and facile insertion of the carbonyl unit using chloroform as an inexpensive CO source in a two-chamber setup. Various value-added pharmaceutically relevant compounds such as CX-516, CX-546, and farampator were synthesized using the technique. Furthermore, the commercially designed COware was engineered to COware-RB setup for sequential one-pot synthesis of indenoisoquinolines (topoisomerase I inhibitors).

Exploiting Coordination Behavior of 7-Azaindole for Mechanistic Investigation of Chan-Lam Coupling and Application to 7-Azaindole Based Pharmacophores.

Multiple spectroscopic techniques, along with single-crystal X-ray analysis, have been used to reveal the detailed structural and electronic information on reaction intermediates of a new copper(II)-DBU catalytic system for the N-arylation of 7-Azaindole. The reaction mixture of Chan-Lam cross-coupling yields two dimeric copper(II)-7-azaindole complexes, including one attached with DBU, prior to adding arylboronic acid and are confirmed structurally and spectroscopically. A suitable mechanism has been proposed using the dimeric copper(II) complex as a catalyst for the coupling reactions. The role of DBU as a base and also as an auxiliary ligand in the course of the reaction has been established. The transmetalated monomeric aryl-copper(II) species generated from the dimeric unit is oxidized by another equivalent of copper(II) to yield an aryl-copper(III) intermediate for facile N-arylation, which has been authenticated with UV-vis spectroscopy. The regeneration of the copper(II)-catalyst by aerial oxidation of colorless copper(I) species (generated via reductive elimination and disproportionation step) is confirmed by mass and absorption spectroscopy. Detailed DFT and TD-DFT calculations help to rationalize the proposed reaction intermediates and their corresponding electronic transitions. Moreover, the confirmation of copper(I)-7-azaindole intermediate via HRMS reaffirmed the involvement of Cu(II)/Cu(III)/Cu(I) species in the Chan-Lam type of coupling. A medicinally-important 7-azaindole-based SHP2 inhibitor has been synthesized via sequential arylation.

CuF2/DMAP-Catalyzed N-Vinylation: Scope and Mechanistic Study.

CuF2/DMAP has been established as an excellent catalytic system for vinylsilane-promoted N-vinylation of amides and azoles at room temperature without an external fluoride source. A mechanism has been proposed on the basis of the isolation of reactive intermediate [Cu(DMAP)4Cl2], fluoride ion-assisted transmetalation, and ultraviolet-visible spectroscopic studies. The catalytic efficiency of the synthesized and structurally characterized [Cu(DMAP)4Cl2] complex has been demonstrated. The valuable monomers for water-soluble polymers, viz., NVP, NVC, and NVIBA, were synthesized on a gram scale.

Ni(II) complexes of a new tetradentate NN'N''O picolinoyl-1,2-phenylenediamide-phenolate redox-active ligand at different redox levels.

Three square planar nickel(II) complexes of a new asymmetric tetradentate redox-active ligand H3L2 in its deprotonated form, at three redox levels, open-shell semiquinonate(1-) π radical, quinone(0) and closed-shell dianion of its 2-aminophenolate part, have been synthesized. The coordinated ligand provides N (pyridine) and N' and N'' (carboxamide and 1,2-phenylenediamide, respectively) and O (phenolate) donor sites. Cyclic voltammetry on the parent complex [Ni(L2)] 1 in CH2Cl2 established a three-membered electron-transfer series (oxidative response at E1/2 = 0.57 V and reductive response at -0.32 V vs. SCE) consisting of neutral, monocationic and monoanionic [Ni(L2)]z (z = 0, 1+ and 1-). Oxidation of 1 with AgSbF6 affords [Ni(L2)](SbF6) (2) and reduction of 1 with cobaltocene yields [Co(η5-C5H5)2][Ni(L2)] (3). The molecular structures of 1·CH3CN, 2·0.5CH2Cl2 and 3·C6H6 have been determined by X-ray crystallography at 100 K. Characterization by 1H NMR, X-band EPR (gav = 2.006 (solid); 2.008 (CH2Cl2-C6H5CH3 glass); 80 K) and UV-VIS-NIR spectral properties established that 1, 2 and 3 have [NiII{(L2)˙2-}], [NiII{(L2)-}]+/1+ and [NiII{(L2)3-}]-/1- electronic states, respectively. Thus, the redox processes are ligand-centred. While 1 possesses paramagnetic St (total spin) = 1/2, 2 and 3 possess diamagnetic ground-state St = 0. Interestingly, the variable-temperature (2-300 K) magnetic measurement reveals that 1 with the St = 1/2 ground state attains the antiferromagnetic St = 0 state at a very low temperature, due to weak noncovalent interactions via π-π stacking. Density functional theory (DFT) electronic structural calculations at the B3LYP level of theory rationalized the experimental results. In the UV-VIS-NIR spectra, broad absorptions are recorded for 1 and 2 in the range of 800-1600 nm; however, such an absorption is absent for 3. Time-dependent (TD)-DFT calculations provide a very good fit with the experimental spectra and allow us to identify the observed electronic transitions.

Iron(III) Complexes of a Hexadentate Thioether-Appended 2-Aminophenol Ligand: Redox-Driven Spin State Switchover.

A green complex [Fe(L3)] (1), supported by the deprotonated form of a hexadentate noninnocent redox-active thioether-appended 2-aminophenolate ligand (H4L3 = N,N'-bis(2-hydroxy-3,5-di-tert-butylphenyl)-2,2'-diamino(diphenyldithio)ethane), has been synthesized and structurally characterized at 100(2) K and 298(2) K. In CH2Cl2, 1 displays two oxidative and a reductive one-electron redox processes at E1/2 values of -0.52 and 0.20 V, and -0.85 V versus the Fc+/Fc redox couple, respectively. The one-electron oxidized 1+ and one-electron reduced 1- forms, isolated as a blackish-blue solid 1(PF6)·CH2Cl2 (2) and a gray solid [Co(η5-C5H5)2]1·DMF (3), have been structurally characterized at 100(2) K. Structural parameters at 100 K of the ligand backbone and metrical oxidation state values unambiguously establish the electronic states as [FeIII{(LAPO,N)2-}{(LISQO,N)•-}{(LS,S)0}] (1) (two tridentate halves are electronically asymmetric-ligand mixed-valency), [FeIII{(LISQO,N)•-}{(LISQO,N)•-}{(LS,S)0}]+ (1+), and [FeIII{(LAPO,N)2-}{(LAPO,N)2-}{(LS,S)0}]- (1-) [dianionic 2-amidophenolate(2-) (LAPO,N)2- and monoanionic 2-iminobenzosemiquinonate(1-) π-radical (Srad = 1/2) (LISQ)•- redox level]. Mössbauer spectral data of 1 at 295, 200, and 80 K reveal that it has a major low-spin (ls)-Fe(III) and a minor ls-Fe(II) component (redox isomers), and at 7 K, the major component exists exclusively. Thus, in 1, the occurrence of a thermally driven valence-tautomeric (VT) equilibrium (asymmetric) [FeIII{(LAPO,N)2-}{(LISQO,N)•-}{(LS,S)0}] ⇌ (symmetric) [FeII{(LISQO,N)•-}{(LISQO,N)•-}{(LS,S)0}] (80-295 K) is implicated. Mössbauer spectral parameters unequivocally establish that 1+ is a ls-Fe(III) complex. In contrast, the monoanion 1- contains a high-spin (hs)-Fe(III) center (SFe = 5/2), as is deduced from its Mössbauer and EPR spectra. Complexes 1-3 possess total spin ground states St = 0, 1/2, and 5/2, respectively, based on 1H NMR and EPR spectra, the variable-temperature (2-300 K) magnetic behavior of 2, and the µeff value of 3 at 300 K. Broken-symmetry density functional theory (DFT) calculations at the B3LYP-level of theory reveal that the unpaired electron in 1+/2 is due to the (LISQ)•- redox level [ls-Fe(III) (SFe = 1/2) is strongly antiferromagnetically coupled to one of the (LISQ)•- radicals (Srad = 1/2)], and 1-/3 is a hs-Fe(III) complex, supported by (L3)4- with two-halves in the (LAP)2- redox level. Complex 1 can have either a symmetric or asymmetric electronic state. As per DFT calculation, the former state is stabilized by -3.9 kcal/mol over the latter (DFT usually stabilizes electronically symmetric structure). Time-dependent (TD)-DFT calculations shed light on the origin of observed UV-vis-NIR spectral absorptions for 1-3 and corroborate the results of spectroelectrochemical experiments (300-1100 nm) on 1 (CH2Cl2; 298 K). Variable-temperature (218-298 K; CH2Cl2) absorption spectral (400-1000 nm) studies on 1 justify the presence of VT equilibrium in the solution-state.

Assisted π-stacking: a strong synergy between weak interactions.

Synergy between a pair of weak non-covalent interactions can predispose a molecular self-assembly towards a specific pathway. We report assisted π-stacking, a synergy between aromatic π-stacking and n →π* interactions that exhibits an unprecedented strength and thermal stability. Natural bond orbital analysis reveals the non-additive nature of the interaction.