Comptes Rendus Chimie p. 816 - 822 (2015)
Update date:2022-08-11
Topics:
Kim, Youngwon
Park, Soonheum
The treatment of [PdL3(NH3)]OTf (L3Combining double low line(PEt3)2(Ph) (1), (2,6-(Cy2PCH2)2C6H3) (3)) with NaNH2 in THF afforded dimeric and monomeric parent-amido palladium(II) complexes with bridging and terminal NH2, respectively, anti-[Pd(PEt3)(Ph)(1/4-NH2)]2 (2) and Pd(2,6-(Cy2PCH2)2C6H3)(NH2) (4). The dimeric complex 2 crystallizes in the space group P21/n with aCombining double low line13.228(2) ?, bCombining double low line18.132(2) ?, cCombining double low line24.745(2) ?, βCombining double low line101.41(1)°, and ZCombining double low line4. It has been found that there are two crystallographically independent molecules with Pd(1)-Pd(2) and Pd(3)-Pd(4) distances of 2.9594 (10) and 2.9401(9) ?, respectively. The monomeric amido complex 4 protonates from trace amounts of water to give the cationic ammine species [Pd(2,6-(Cy2PCH2)2C6H3)(NH3)]+. Complex 4 reacts with diphenyliodonium triflate ([Ph2I]OTf) to give aniline complex [Pd(2,6-(Cy2PCH2)2C6H3)(NH2Ph)]OTf (5). Reaction of 4 with dialkyl acetylenedicarboxylate (DMAD, DEAD) yields diastereospecific palladium(II) vinyl derivative (Z)-(Pd(Cy2PCH2)2C6H3)(CRCombining double low lineCR(NH2)) (RCombining double low lineCO2Me (6a), CO2Et (6b)). Reacting complexes 6a and 6b with p-nitrophenol produces (Pd(Cy2PCH2)2C6H3)(OC6H4-p-NO2) (8) and cis-CHRCombining double low lineCR(NH2), exclusively.
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