The effects of Li+ and Mg2+ on the electrochemical behaviour and photoreduction of N,N′-bis(2,6-diisopropylphenyl)naphthalene diimide (Dipp2NDI) have been investigated using cyclic voltammetry and UV-vis spectroscopy. Strong cation–anion interactions between Li+ or Mg2+ and [Dipp2NDI]2− result in solvent-dependent anodic shifts of the NDI˙−/2− redox couple. In organic solvents of moderate dielectric constant and donor ability, the two, one-electron redox processes typically observed for Dipp2NDI merge into a single, two-electron process. This strong metal cation effect has been leveraged for the photoreduction of Dipp2NDI to [Dipp2NDI]2−via a disproportionation process. Chemical reduction of Dipp2NDI with iPrMgCl has allowed the isolation of Mg2+ complexes of [Dipp2NDI]2−. Single crystal X-ray diffraction was used to determine the structure of a dimeric complex, [(Dipp2NDI)Mg2(THF)3]2, that features strong coordination of Mg2+ by the oxygen atoms of the reduced NDI.

A porous metal–organic framework Zr6O4(OH)4(L-PdX)3 (1-X) has been constructed from Pd diphosphinite pincer complexes ([L-PdX]4– = [(2,6-(OPAr2)2C6H3)PdX]4–, Ar = p-C6H4CO2–, X = Cl, I). Reaction of 1-X with PhI(O2CCF3)2 facilitates I–/CF3CO2– ligand exchange to generate 1-TFA and I2 as a soluble byproduct. 1-TFA is an active and recyclable catalyst for transfer hydrogenation of benzaldehydes using formic acid as a hydrogen source. In contrast, the homogeneous analogue tBu(L-PdTFA) is an ineffective catalyst owing to decomposition under the catalytic conditions, highlighting the beneficial effects of immobilization.

The dinuclear gold(II,II) and gold(III,III) complexes [Au2(μ-PY)2(MeCN)2]OTf2 (2-OTf2) and [Au2(μ-PY)2(μ-CH2)(MeCN)2]OTf2 (3-OTf2) (PY = [(CH2)2PPh2]−) have been synthesized and evaluated as Lewis acid catalysts for Mukaiyama addition and alkyne hydroamination reactions. 2-OTf2 and 3-OTf2 provide similar or improved catalytic activity for these reactions compared to the commonly used gold(I) Lewis acids Ph3PAuOTf and IPrAuOTf. The versatile Lewis acidity of 2-OTf2 was further demonstrated by its superior performance in a cascade reaction involving intramolecular hydroamination followed by intermolecular conjugate addition to generate a 2,3-substituted indole.

The effects of Li+ and Mg2+ on the electrochemical behaviour and photoreduction of N,N′-bis(2,6-diisopropylphenyl)naphthalene diimide (Dipp2NDI) have been investigated using cyclic voltammetry and UV-vis spectroscopy. Strong cation–anion interactions between Li+ or Mg2+ and [Dipp2NDI]2− result in solvent-dependent anodic shifts of the NDI˙−/2− redox couple. In organic solvents of moderate dielectric constant and donor ability, the two, one-electron redox processes typically observed for Dipp2NDI merge into a single, two-electron process. This strong metal cation effect has been leveraged for the photoreduction of Dipp2NDI to [Dipp2NDI]2−via a disproportionation process. Chemical reduction of Dipp2NDI with iPrMgCl has allowed the isolation of Mg2+ complexes of [Dipp2NDI]2−. Single crystal X-ray diffraction was used to determine the structure of a dimeric complex, [(Dipp2NDI)Mg2(THF)3]2, that features strong coordination of Mg2+ by the oxygen atoms of the reduced NDI.