The complex (iPr3P) Ni (η2-Bu3SnCHCH2) 2 (1a) was characterized by NMR spectroscopy and was identified as the active species for catalytic C–H bond stannylation of partially fluorinated aromatics, for example in the reaction between pentafluorobenzene and Bu3SnCHCH2, which generates C6F5SnBu3 and ethylene. The crystalline complex (iPr3P) Ni (η2-Ph3SnCHCH2) 2 (1b) provides a more easily handled analogue, and is also ...