The robust, high-valent Ni complex [(Py) Ni F (CF ) ] (Py=pyridine) was synthesized and fully characterized by NMR spectroscopy, X-ray diffraction, and elemental analysis. It reacts with aromatic compounds at 25 °C to form the corresponding benzotrifluorides in nearly quantitative yield. The monomeric and dimeric Ni CF complexes 2⋅Py and 2 were identified as key intermediates, and their structures were unambiguously determined by EPR spectroscopy and X-ray diffraction. Preliminary kinetic studies in combination with the isolation of reaction intermediates confirmed that the C-H bond-breaking/C-CF bond-forming sequence can occur both at Ni CF and Ni CF centers.

The reactivity of amidinate (1a,b, 2a)-or NHC (5a,b)-stabilized germanium(II) compounds toward diiron nonacarbonyl has been investigated. These germylenes act as two-electron carbene-like ligands and lead to stable germylene iron complexes by exchange reaction of a carbonyl ligand. Whereas the amidinato chloro germylenes lead to stable complexes, a bis(iron germylene) oxide was obtained from the bis-amidinato germylene. The reactions of NHC-stabilized germylenes (5a,b) with Fe 2 (CO) 9 were also explored, giving donor−acceptor complexes of germylenes. All the germanium−iron complexes were fully characterized ( 1 H and 13 C NMR and IR) including by single-crystal X-ray diffraction structure determinations.