The reaction of [PdCl{C6H3(CH2NMe2)2-2,6}] ([PdCl(NCN)]) with either the sodium or silver salts of the borate anions [B{C6H4(SiMe3)-4}4]- and [B(C6H4{SiMe2(CH2CH2C6F13)}-4)4]- under various reaction conditions resulted in the exclusive formation of the respective dinuclear [{Pd(NCN)}2(μ-Cl)][B{C6H4(SiMe2R)-4}4] salts 4a (R = Me) and 4b (R = CH2CH2C6F13). When using BF4 -, both dinuclear [{Pd(NCN)}2(μ-Cl)]BF4 (4c) and mononuclear [Pd(NCN)(OH2)]BF4 (5c) could be obtained. The molecular structure of 5c showed the presence of hydrogen-bridging interactions between coordinated H2O molecules and the fluorine atoms of BF4 -. Attempts to isolate complexes of the type [Pd(NCN)(OH2)][B{C6H4(SiMe2R)-4}4] were unsuccessful. This has been ascribed to a difference in stabilization of the respective mono- and dinuclear cations by the borate anions BF4 - and [B{C6H4(SiMe2R)-4}4]-, respectively. The conclusions are supported by DFT calculations.