The treatment of [PdL 3 (NH 3 )](OTf) n ( n = 1; L 3 = (PEt 3 ) 2 (Ph), (2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 ), n = 2; L 3 = (dppe)(NH 3 )) with NaNH 2 in tetrahydrofuran at ambient temperature or −78 °C afforded the dimeric and monomeric parent-amido palladium(II) complexes anti -[Pd(PEt 3 )(Ph)(μ-NH 2 )] 2 ( 1 ), [Pd(dppe)(μ-NH 2 )] 2 (OTf) 2 ( 2 ), and Pd(2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 )(NH 2 ) ( 3 ), respectively. The molecular structures of the amido-bridged (μ-NH 2 ) dimeric complexes 1 and 2 were determined by single-crystal X-ray crystallography. The monomeric amido complex 3 reacted with trace amounts of water to give a hydroxo complex, Pd(2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 )(OH) ( 4 ). Exposing complex 3 to an excess of water resulted in the complete conversion of the complex into two species [Pd(2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 )(OH 2 )] + and [Pd(2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 )(NH 3 )] + . Complex 3 reacted with diphenyliodonium triflate ([Ph 2 I]OTf) to give the aniline complex [Pd(2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 )(NH 2 Ph)]OTf. The reaction of 3 with phenylacetylene (HC CPh) yielded a palladium(II) acetylenide Pd(2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 )(C CPh) ( 5 ), quantitatively, along with the liberation of ammonia. The reaction of 3 with dialkyl acetylenedicarboxylate yielded diastereospecific palladium(II) vinyl derivatives ( Z )-Pd(2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 )(CR CR(NH 2 )) (R = CO 2 Me ( 6a ), CO 2 Et ( 6b )). The reaction of complexes 6a and 6b with p -nitrophenol produced Pd(2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 )(OC 6 H 4 - p -NO 2 ) ( 7 ) and cis -CHR CR(NH 2 ), exclusively. Reactions of 3 with either dialkyl maleate ( cis -(CO 2 R)CH CH(CO 2 R)) (R = CH 3 , CH 2 CH 3 ) or cis -stilbene ( cis -CHPh CHPh) did not result in any addition product. Instead, isomerization of the cis -isomers to the trans -isomers occurred in the presence of catalytic amounts of 3 . Complex 3 reacted with a stoichiometric amount of acrylonitrile (CH 2 CHCN) to generate a metastable insertion product, Pd(2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 )(CH(CN)CH 2 NH 2 ). On the other hand, the reaction of 3 with an excess of acrylonitrile slowly produced polymeric species of acrylonitrile. The catalytic hydroamination of olefins with NH 3 was examined in the presence of Pd(2,6-(Cy 2 PCH 2 ) 2 C 6 H 3 )(OTf), producing a range of hydroaminated products of primary, secondary, and tertiary amines with different molar ratios of more than 99% overall yield. A mechanistic feature for the observed catalytic hydroamination is described with regard to the aminated derivatives of palladium(II).