Koyu Fujita

Thioether-ligated nickel(I) complexes for the activation of dioxygen

The preparation of phenyltris[1-adamantyl(thiomethyl)]borate [PhTtAd], which incorporates the large 1-adamantyl thioether substituent, is described. This derivative was sought to permit the preparation of four-coordinate nickel(I) complexes. Following a synthetic scheme for the related tert-butyl ligand, [PhTtBut], the following complexes were prepared and characterized fully, [PhTtAd]Ni(CO), [PhTtAd]Ni(PMe3) and [κ2-PhTtAd]Ni(η2-CH2SAd). The last species is a degradation product resulting from attempted reduction of the nickel(II) precursor, [PhTtAd]NiCl, in the absence of a ligand suitable for trapping the nickel(I) fragment.

Mixed metal bis(-oxo) complexes with [CuM(-O)2]n+ (M = Ni(iii) or Pd(ii)) coresElectronic supplementary information (ESI) available: experimental and calculation details. See http://www.rsc.org/suppdata/cc/b4/b404640d/

Two highly reactive heterodinuclear bis(μ-oxo) complexes were prepared by combining mononuclear peroxo species with reduced metal precursors at −80 °C and were identified by UV-vis, EPR/NMR, and resonance Raman spectroscopy, with corroboration in the case of the CuPd system from density functional calculations.