Inorganic reaction mechanisms. A personal journey

Abstract

This review describes a personal journey over the past two decades highlighting experimental and computational mechanistic studies in inorganic chemistry performed with numerous PhD students, post-docs, visiting scientists and colleagues from abroad.

Mechanistic Studies on the Reaction between Aquacobalamin and the HNO Donor Piloty’s Acid over a Wide pH Range in Aqueous Solution

“…The kinetics of the reaction between CblOH 2 + and PA with the PA concentration in excess compared to the concentration of CblOH 2 + was also studied at lower pH conditions. A preliminary report on this work was recently included in an extended Perspective article for Dalton Transactions . In this work, a buffered anaerobic solution of CblOH 2 + (0.10 M Tris buffer pH 7.2, 25 °C, Ar atmosphere) was added to an aqueous anaerobic solution of PA. Changes in the UV–vis spectrum were recorded using a stopped-flow instrument.…”

“…A preliminary report on this work was recently included in an extended Perspective article for Dalton Transactions. 53 In this work, a buffered anaerobic solution of CblOH 2 + (0.10 M Tris buffer pH 7.2, 25 °C, Ar atmosphere) was added to an aqueous anaerobic solution of PA. Changes in the UV−vis spectrum were recorded using a stopped-flow instrument. Figures 9a and S11a show typical UV−vis spectral changes for the reaction of CblOH 2 + (λ max = 275, 351, 412, 497, 525 nm) with excess PA. Once again CblNO is formed (λ max = 321, 480 nm 26,38 ), and three isosbestic points were observed at 340, 367, and 498 nm.…”

Electronic effects on the mechanism of the NAD+ coenzyme reduction catalysed by a non-organometallic ruthenium(ii) polypyridyl amine complex in the presence of formate

“…These complexes are by one or two orders of magnitude less labile than the en analogue, for the aquation and water substitution reactions by chloride and thiourea at 25 °C, respectively. 28 …”

“…We concluded that the rate of displacing a monodentate ligand, the rst step of the proposed mechanism of the catalytic NAD + -NADH conversion, depends on the electronic and steric effects provided by bidentate ligands. [25][26][27][28] Based on these studies, we expect that the catalytic efficiency will depend markedly on the nature of the coordinated bidentate ligand. The same effect was also observed for organometallic complexes studied by Sadler et al 17,18,21 Therefore, we extended our work to the [Ru II (terpy)(ampy)Cl]Cl (ampy ¼ 2-(aminomethyl)pyridine) and [Ru II (terpy)(bipy)Cl]Cl$2H 2 O (bipy ¼ 2,2 0 -bipyridine) complexes.…”

Complexation and bonding studies on [Ru(NO)(H2O)5]3+ with nitrate ions by using density functional theory calculation

“…16 Density functional theory (DFT) calculations have been employed to interpret experimental results and to understand the coordination character of PGM complexes. 17,18 Recently, the DFT applications to the Rh and Pd complexes with H 2 O and NO 3 À ligands, considering the geometrical isomers for the unidentate system, have been reported by combining them with experimental techniques. 19,20 Watanabe et al studied the coordination bond lengths and electronic transitions of [Pd(NO 3 )-…”