The reaction of Me3SiCH2I with [Pd(IfBu) 2](IfBu = 1,3-di-ferf-butyl-imidazol-2-ylidene) results, not in simple oxidative addition, but in carbon-silicon bond activation and formation of [Pd(Me3Si)(KBu)(μ-I)]2 (2) and [Pd(CH 2ItBu)I2](3). The zwitterionic nature of the latter has been confirmed by DFT studies, and a possible mechanism for the formation of these two unexpected products is presented. Complex 2 has also been synthesised independently by the direct oxidative addition of Me3SiI to [Pd(ItBu)2]. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009.