| Abstract
| - The reaction of [PdCl{C6H3(CH2NMe2)2-2,6}] ([PdCl(NCN)]) with either the sodium or silversalts 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 respectivedinuclear [{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 thepresence of hydrogen-bridging interactions between coordinated H2O molecules and thefluorine 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 ofthe respective mono- and dinuclear cations by the borate anions BF4- and [B{C6H4(SiMe2R)-4}4]-, respectively. The conclusions are supported by DFT calculations.
- Reaction of [PdCl{C6H3(CH2NMe2)2-2,6}] with Ag[B{C6H4(SiMe3)-4}4] and Ag[B{C6H4(SiMe2CH2CH2C6F13)-4}4] resulted in the exclusive formation of [{Pd(NCN)}2(μ-Cl)][B{C6H4(SiMe2R)-4}4] (R = Me and CH2CH2C6F13), whereas AgBF4 yields [{Pd(NCN)}2(μ-Cl)]BF4 and [Pd(NCN)(OH2)]BF4. The inability to obtain dinuclear complexes with the tetraarylborate anion is explained by a difference in stabilization of the mono- and dinuclear cations by the borate anions BF4- and [B{C6H4(SiMe2R)-4}4]-. The conclusions are supported by DFT calculations.
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