Falvello Larry R., Fernández Susana, Navarro Rafael, Rueda Angel, Urriolabeitia Esteban P.
Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza- Consejo Superior de Investigaciones Científicas, 50009 Zaragoza, Spain.
Inorg Chem. 1998 Nov 16;37(23):6007-6013. doi: 10.1021/ic980392z.
The reaction of Pd(OAc)(2) with the bis(phosphonium) salt [Ph(3)PCH(2)COCH(2)PPh(3)]Cl(2) (1:1 molar ratio) results in the formation of the cis-dichlorobis(ylide) derivative Cl(2)Pd{C(H)PPh(3)CO}, 1, in which the bis(ylide) ligand C(H)PPh(3)CO acts as a chelating group through the two ylide carbon atoms. Complex 1 reacts with TlClO(4) (1:1 molar ratio) to give Pd(&mgr;-Cl){C(H)PPh(3)CO}(ClO(4))(2), 2, which reacts with two further equivalents of TlClO(4) in NCMe to give Pd{C(H)PPh(3)CO}(NCMe)(2)(2) 3. The reactivity of 2 and 3 has been explored. Compound 2 reacts with pyridine, 3,5-lutidine, or Ph(3)P=C(H)CN (1:2 molar ratio), resulting in the rupture of the chlorine bridging system and formation of PdCl{C(H)PPh(3)CO}(L) (L = py (4), 3,5-lu (5), NC-C(H)=PPh(3) (6)), and with Tlacac (1:2 molar ratio) with formation of the acetylacetonate Pd(acac){C(H)PPh(3)CO}, 7. On the other hand, complex 3 reacts with the ylide Ph(3)P=C(H)CN (1:2 molar ratio) giving Pd{C(H)PPh(3)CO}NC-C(H)=PPh(3)(2), 8, which contains two N-coordinated ylides, and with NBu(4)OH (1:1) to give Pd(&mgr;-OH){C(H)PPh(3)CO}(ClO(4))(2), 9. The reaction of Pd(OAc)(2) with the ylide phosphonium salt Ph(3)P=C(H)COCH(2)PPh(3) (1:1) gives the acetate dimer Pd(&mgr;-OOCCH(3)){C(H)PPh(3)CO}(ClO(4))(2), 10. The structures of complexes 1-10 were deduced from their spectroscopic data and from the resolution of the molecular structure of complex 2.CH(2)Cl(2).
醋酸钯（II）与双（鏻）盐[Ph₃PCH₂COCH₂PPh₃]Cl₂（摩尔比1:1）反应生成顺式二氯双（叶立德）衍生物Cl₂Pd{[C(H)PPh₃]₂CO}（1），其中双（叶立德）配体[C(H)PPh₃]₂CO通过两个叶立德碳原子作为螯合基团。配合物1与高氯酸铊（摩尔比1:1）反应生成[Pd(μ-Cl){[C(H)PPh₃]₂CO}]₂(ClO₄)₂（2），其在N,N-二甲基甲酰胺中再与两当量的高氯酸铊反应生成Pd{[C(H)PPh₃]₂CO}(NCMe)₂₂（3）。对2和3的反应活性进行了研究。化合物2与吡啶、3,5-二甲基吡啶或Ph₃P=C(H)CN（摩尔比1:2）反应，导致氯桥连体系断裂并形成PdCl{[C(H)PPh₃]₂CO}(L)（L = py（4），3,5-lu（5），NC-C(H)=PPh₃（6）），与乙酰丙酮铊（摩尔比1:2）反应生成乙酰丙酮化物Pd(acac){[C(H)PPh₃]₂CO}（7）。另一方面，配合物3与叶立德Ph₃P=C(H)CN（摩尔比1:2）反应生成Pd{[C(H)PPh₃]₂CO}[NC-C(H)=PPh₃]₂₂（8），其含有两个N配位的叶立德，与四丁基氢氧化铵（摩尔比1:1）反应生成[Pd(μ-OH){[C(H)PPh₃]₂CO}]₂(ClO₄)₂（9）。醋酸钯（II）与叶立德鏻盐Ph₃P=C(H)COCH₂PPh₃（摩尔比1:1）反应生成醋酸盐二聚体[Pd(μ-OOCCH₃){[C(H)PPh₃]₂CO}]₂(ClO₄)₂（10）。配合物1 - 10的结构通过它们的光谱数据以及配合物2·CH₂Cl₂分子结构的解析推导得出。
