Pendulum-like hemilability in a Ti-based frustrated Lewis Trio.

We describe the first experimental example of a theoretically predicted Frustrated Lewis Trio (FLT). A tetradentate PNNP ligand is used to stabilise a highly electrophilic [TiCl] fragment in a way that results in two equally long and frustrated Ti-P bonds. A combined experimental and computational approach revealed a distinct role of each Lewis basic phosphine in the heterolytic activation of chemical bonds.

Mechanistic Investigations into the Selective Reduction of Oxygen by a Multicopper Oxidase T3 Site-Inspired Dicopper Complex.

Understanding how multicopper oxidases (MCOs) reduce oxygen in the trinuclear copper cluster (TNC) is of great importance for development of catalysts for the oxygen reduction reaction (ORR). Herein, we report a mechanistic investigation into the ORR activity of the dinuclear copper complex ( = 2,7-bis[bis(2-pyridylmethyl)aminomethyl]-1,8-naphthyridine). This complex is inspired by the dinuclear T3 site found in the MCO active site and confines the Cu centers in a rigid scaffold.

α-Diimine synthesis titanium-mediated multicomponent diimination of alkynes with C-nitrosos.

α-Diimines are commonly used as supporting ligands for a variety of transition metal-catalyzed processes, most notably in α-olefin polymerization. They are also precursors to valuable synthetic targets, such as chiral 1,2-diamines. Their synthesis is usually performed through acid-catalyzed condensation of amines with α-diketones.

Cooperative H Activation on Dicopper(I) Facilitated by Reversible Dearomatization of an "Expanded PNNP Pincer" Ligand.

A naphthyridine-derived expanded pincer ligand is described that can host two copper(I) centers. The proton-responsive ligand can undergo reversible partial and full dearomatization of the naphthyridine core, which enables cooperative activation of H giving an unusual butterfly-shaped Cu H complex.