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  1. Herein, the pyridinophanetetradentate ligand 3,6,9-trimethyl-3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene, PyNMe 3 , is used to isolate and structurally characterize well-defined organometallic Ni( ii ) and Ni( iii ) complexes bearing the cycloneophyl fragment, an alkyl/aryl C-donor ligand. Furthermore, spectroscopic and cryo-mass spectrometry studies suggest the formation of a transient Ni( iv ) organometallic complex, and its relevance to C–C and C–O bond formation reactivity studies is discussed. 
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