Dimeric and monomeric palladium(II) parent-amido (NH2) complexes: Synthesis, characterization, and reactivity - 30/07/15
pages | 7 |
Iconographies | 4 |
Vidéos | 0 |
Autres | 0 |
Abstract |
The treatment of [PdL3(NH3)]OTf (L3=(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)(μ-NH2)]2 (2) and Pd(2,6-(Cy2PCH2)2C6H3)(NH2) (4). The dimeric complex 2 crystallizes in the space group P21/n with a=13.228(2) Å, b=18.132(2) Å, c=24.745(2) Å, β=101.41(1)°, and Z=4. 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) Å, 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)(CR=CR(NH2)) (R=CO2Me (6a), CO2Et (6b)). Reacting complexes 6a and 6b with p-nitrophenol produces (Pd(Cy2PCH2)2C6H3)(OC6H4–p-NO2) (8) and cis-CHR=CR(NH2), exclusively.
Le texte complet de cet article est disponible en PDF.Keywords : Parent–amido palladium, C-N bond formation, Syn-insertion, Diastereospecific insertion of the CC into the Pd-N bond, X-ray crystal structure
Plan
Vol 18 - N° 8
P. 816-822 - août 2015 Retour au numéroBienvenue sur EM-consulte, la référence des professionnels de santé.
L’accès au texte intégral de cet article nécessite un abonnement.
Bienvenue sur EM-consulte, la référence des professionnels de santé.
L’achat d’article à l’unité est indisponible à l’heure actuelle.
Déjà abonné à cette revue ?