Themed collection Inorganic Reaction Mechanisms

Sam de Visser, Jonathan Rourke and Kylie Vincent introduce this Dalton Transactions themed collection on inorganic reaction mechanisms.

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.

Bimetallic “baguette” versions of the popular CpRh(I) “sandwich” complexes have been synthesised with a tetraarylated pentalenide. The factors leading to syn versus anti metallation have been investigated and the scope of ligand substitution is explored.

A ruthenium phthalocyanine catalyzes the cyclopropanation of olefins (15 substr.) and single carbene insertion into N–H bonds of aromatic, heteroaromatic and aliphatic amines (20 substr.) with high selectivity and under practical reaction conditions.

KS-DFT and MSDFT studies reveal a novel CEPT step that triggers ring contraction of piperidines by P450.

Quite different reaction mechanisms were observed in a kinetic study of NO binding to iron(II) complexes.

Density functional methods are applied to explore the reaction mechanism for CO₂ hydrogenation to methanol over low-index Cu surfaces, namely Cu(110) and Cu(100).

A comparative spectroscopic and computational study of reactivity between ferryl-tosylimido and ferryl-oxo complexes of two biomimetic model systems. The Fe(IV)-tosylimido complex was found to be sluggish in comparison to its fellow oxo counterpart.

The synthesis, spectroscopic characterization and DFT calculations of a tetranuclear cobalt complex supported on a stannoxane core, and its catalytic O₂-reduction ability are reported.

Photolysis of [Mn(C^N)(CO)₄] (C^N = bis-(4-methoxyphenyl)methanimine) in heptane solution results in ultra-fast CO dissociation and ultimate formation of a rare Mn-containing dinitrogen complex fac-[Mn(C^N)(CO)₃(N₂)].

This work reports on the synthesis and characterization of a series of mononuclear thiosemicarbazone nickel complexes that display significant catalytic activity for hydrogen production in DMF using trifluoroacetic acid as the proton source.

Crystal structures and computational results reveal how Hyoscyamine 6β-hydroxylase targets its oxidative power at the C6 position of the tropane ring while sparing the nearby C7 site.

A detailed QM/MM and DFT study into the structure and reactivity of AlkB repair enzymes with alkylated DNA bases is reported. In particular, we investigate the aliphatic hydroxylation and CC epoxidation mechanisms of the enzymes by a high-valent iron(IV)–oxo intermediate.

A commercially available iron readily engages in catalytic Si–O and Si–N bond formation under visible light irradiation.

The iron(IV)oxido complex [(bispidine)Fe^IVO(Cl)]⁺ is shown by experiment and high-level DLPNO-CCSD(T) quantum-chemical calculations to be an extremely short-lived and very reactive intermediate-spin (S = 1) species.

The dioxygenation of nitriles by [Co^III(TBDAP)(O₂)]⁺ (TBDAP = N,N-di-tert-butyl-2,11-diaza[3.3](2,6)-pyridinophane) is investigated using DFT-calculations.

Kinetic and thermodynamic selectivities are opposite: steric and electronic factors control ortho : para selectivity (R²).

Pt-catalyzed direct coupling of benzene to biphenyl using PhI(OAc)₂ as an oxidant in the absence of any acid as a co-solvent or co-catalyst was mechanistically investigated.

This work describes the identification of two residues, D137 and E62, that are critical for, respectively, the transport of Fe²⁺ into, and Fe³⁺ out of, the catalytic sites of a prokaryotic ferritin.

A subtle positional shift of the distal haem pocket aspartate in two dye decolourising peroxidase homologs has a remarkable effect on their reactivity with H₂O₂.

A scandium hydridoborate complex supported by the dianionic pentadentate ligand B₂Pz₄Py is prepared via hydride abstraction from the previously reported scandium hydride complex with tris-pentafluorophenyl borane.

An Fe^II complex reacts with excess H₂O₂ in the presence of sub-stoichiometric NEt₃ to give Fe^IV(O) and Fe^III(OOH) reactive species following a base-dependent and a base-independent pathway, respectively.

Density functional theory calculations on vanadium-oxo and -peroxo porphyrins are reported and show these systems to be versatile oxidants.

The kinetics of oxidation of different biologically-active Fe^II bis-thiosemicarbazone complexes in water has been monitored at varying dioxygen concentration, temperature, pressure, and pH.

Computations suggest how the substrate binds within the active site and what is the mechanism of an endoperoxide ring formation.

Cationic σ-dihydrogen, σ-amine-borane and neutral hydride complexes, based upon {Rh(PONOP)}, are all shown play a role in the dehydrocoupling of H₃B·NMe₂H. Movement between the three is promoted by free amine, NMe₂H.