Distinct Reactivity Modes of a Copper Hydride Enabled by an Intramolecular Lewis Acid.

We disclose a 1,4,7-triazacyclononane (TACN) ligand featuring an appended boron Lewis acid. Metalation with Cu(I) affords a series of tetrahedral complexes including a boron-capped cuprous hydride. We demonstrate distinct reactivity modes as a function of chemical oxidation: hydride transfer to CO2 in the copper(I) state and oxidant-induced H2 evolution as well as alkyne reduction.

Substrate Specific Metal-Ligand Cooperative Binding: Considerations for Weak Intramolecular Lewis Acid/Base Pairs.

Metal-ligand cooperative binding modes were interrogated in a series of zinc bis(thiophenoxide) complexes. A weak B-S binding interaction is observed in solution between the weakly Lewis basic thiophenoxide ligands and an appended trialkylborane. The energy of this binding event is dependent upon the strength of the Lewis acid and its proximity to the zinc thiophenoxide.

Mobility of Lewis acids within the secondary coordination sphere: toward a model for cooperative substrate binding.

Distance dependence of appended Lewis acids in N2H4 binding and deprotonation was evaluated within a series of zinc complexes. Variation of spacer-length to a tethered trialkylborane Lewis acid revealed distinct preferences for binding and stabilization of the resulting deprotonated N2H3- unit.

Tetrahedral iron featuring an appended Lewis acid: distinct pathways for the reduction of hydroxylamine and hydrazine.

We present the preparation of a nitrogen-based bidentate ligand featuring an appended boron Lewis acid as well as its tetrahedral Fe2+ and Zn2+ complexes. These complexes act as platforms for hydrazine and hydroxylamine capture and reduction chemistry.

Dual oxidase/oxygenase reactivity and resonance Raman spectra of {Cu3O2} moiety with perfluoro-t-butoxide ligands.

A Cu(i) fully fluorinated O-donor monodentate alkoxide complex, K[Cu(OC4F9)2], was previously shown to form a trinuclear copper-dioxygen species with a {Cu3(µ3-O)2} core, TOC4F9, upon reactivity with O2 at low temperature. Herein is reported a significantly expanded kinetic and mechanistic study of TOC4F9 formation using stopped-flow spectroscopy. The TOC4F9 complex performs catalytic oxidase conversion of hydroquinone (H2Q) to benzoquinone (Q). TOC4F9 also demonstrated hydroxylation of 2,4-di-tert-butylphenolate (DBP) to catecholate, making TOC4F9 the first trinuclear species to perform tyrosinase (both monooxygenase and oxidase) chemistry. Resonance Raman spectra were also obtained for TOC4F9, to our knowledge, the first such spectra for any T species. The mechanism and substrate reactivity of TOC4F9 are compared to those of its bidentate counterpart, TpinF, formed from K[Cu(pinF)(PR3)]. The monodentate derivative has both faster initial formation and more diverse substrate reactivity.