Synthesis and Structure of Pd(II) Complexes Containing the C,C-Chelating Bis-Ylide Ligand [Ph(3)P=C(H)](2)CO. X-ray Crystal Structure of {Pd(&mgr;-Cl){[C(H)PPh(3)](2)CO}}(2)(ClO(4))(2).CH(2)Cl(2).
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)](2)CO}, 1, in which the bis(ylide) ligand [C(H)PPh(3)](2)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)](2)CO}](2)(ClO(4))(2), 2, which reacts with two further equivalents of TlClO(4) in NCMe to give [Pd{[C(H)PPh(3)](2)CO}(NCMe)(2)](ClO(4))(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)](2)CO}(L)](ClO(4)) (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)](2)CO}](ClO(4)), 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)](2)CO}[NC-C(H)=PPh(3)](2)](ClO(4))(2), 8, which contains two N-coordinated ylides, and with NBu(4)OH (1:1) to give [Pd(&mgr;-OH){[C(H)PPh(3)](2)CO}](2)(ClO(4))(2), 9. The reaction of Pd(OAc)(2) with the ylide phosphonium salt [Ph(3)P=C(H)COCH(2)PPh(3)](ClO(4)) (1:1) gives the acetate dimer [Pd(&mgr;-OOCCH(3)){[C(H)PPh(3)](2)CO}](2)(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).
Falvello
Larry R.
LR
Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza- Consejo Superior de Investigaciones Científicas, 50009 Zaragoza, Spain.
Fernández
Susana
S
Navarro
Rafael
R
Rueda
Angel
A
Urriolabeitia
Esteban P.
EP