Dehydrogenative Coupling for Synthesis of Quinazolin-4(3H)-ones via Tandem Reaction using Ruthenium(II)-Phenyl-Azo-Naphthaldoxime: An Experimental and Theoretical Investigation.

The bidentate N, N, donor phenyl-azo-naphthaldoxime NpLH, 1 was used to synthesize the ruthenium(II) complex trans-[Ru(NpL)(CO)Cl(PPh)], 2. It has been characterized by SCXRD, electrochemical and spectral studies. Computational analysis indicates that the low-lying π*-LUMO of the complex has substantial azo-character of coordinated ligand.

Electron transfer catalysis mediated by 3d complexes of redox non-innocent ligands possessing an azo function: a perspective.

It was first reported almost two decades ago that ligands with azo functions are capable of accepting electron(s) upon coordination to produce azo-anion radical complexes, thereby exhibiting redox non-innocence. Over the past two decades, there have been numerous reports of such complexes along with their structures and diverse characteristics. The ability of a coordinated azo function to accept one or more electron(s), thereby acting as an electron reservoir, is currently employed to carry out electron transfer catalysis since they can undergo redox transformation at mild potentials due to the presence of energetically accessible energy levels.

Azo-oximate metal-carbonyl to metallocarboxylic acid the intermediate Ir(III) radical congener: quest for co-ligand driven stability of open- and closed-shell complexes.

The redox non-innocent behavior of the diaryl-azo-oxime ligand L1 has been accentuated the synthesis of metastable anion radical complexes of type -[Ir(L)Cl(CO)(PPh)] 2 (CO is to azo group of the ligand) by the oxidative coordination reaction of 1 with Vaska's complex. The stereochemical role of co-ligands the interplay of π-bonding has been found to be decisive in controlling the aptitude of the coordinated redox non-innocent ligand to accept or reject an electron. This has been clarified the isolation of quite a few complexes as well as the failure to synthesize some others.

Ambient-Stable Bis-Azoaromatic-Centered Diradical [(L)M(L)] Complexes of Rh(III): Synthesis, Structure, Redox, and Spin-Spin Interaction.

Bis-azoaromatic electron traps, viz. 2-(2-pyridylazo)azoarene 1, have been synthesized by colligating electron-deficient pyridine and azoarene moieties, and they act as apposite proradical templates for the formation of stable open-shell diradical complexes [(1)Rh(1)] ([2]), starting from the low-valent electron reservoir [Rh]. The less stable monoradical [Rh(1)Cl(PPh)] (3) has also been isolated as a minor product.

Iridium(III) Mediated Reductive Transformation of Closed-Shell Azo-Oxime to Open-Shell Azo-Imine Radical Anion: Molecular and Electronic Structure, Electron Transfer, and Optoelectronic Properties.

The hydrogen bonded bis azo-oximato [IrCl2(L(NOH))(L(NO))] 2 and its deprotonated form (Et3NH)[IrCl2(L(NO))2] (Et3NH)(+)3(-) have been isolated in the crystalline state by a facile synthetic method. The azo-oxime frameworks in 3(-) have been conveniently transformed to the azo-imine by reduction with NaBH4 or ascorbic acid. Notably, the coordinated azo-imines accept an extra electron thereby furnishing the azo-imine radical anion complex 4.

Molecular and electronic structure of nonradical homoleptic pyridyl-azo-oxime complexes of cobalt(III) and the azo-oxime anion radical congener: an experimental and theoretical investigation.

The reaction between a potential flexidentate pyridyl-azo-oxime HL1 and Co(ClO4)2 yields novel homoleptic complexes of types [Co(III)(L(-I))3], 2 and [Co(III)(L(-I))2]ClO4, 3⁺ClO₄ in N6 and N4O2 coordination environments respectively. The FMOs of these complexes vary appreciably and are strongly modified by the coordination environment. This has striking influences on the spectral and redox properties of the metallo conjugates of ligand HL.

Regiospecific Oximato Coordination at the Oxygen Site: Ligand Design and Low-Spin Mn(II) and Fe(II/III) Species.

The (pyridylazo)oxime ligand (C(5)H(4)N)N=NC(=NOH)C(6)H(4)R(p), HRL (R = H, Me), has been synthesized with the objective of promoting the very rare mononuclear oximato-O coordination. The synthesis involves hydrazone nitrosation. HRL reacts with M(ClO(4))(2).