344863-11-2Relevant academic research and scientific papers
Synthesis of terminal and bridging acetonyl complexes of palladium(II). See abstract
Ruiz, José,Rodríguez, Venancio,Cutillas, Natalia,Pardo, Mercedes,Pérez, José,López, Gregorio,Chaloner, Penny,Hitchcock, Peter B.
, p. 1973 - 1982 (2001)
The reaction of the palladium-hydroxo complex [{(o-C6H4CH2NMe2)Pd}2 (μ-OH)2] with acetone leads to the formation of the bridging O,C-acetonyl complexes [{(o-C6H4CH2NMe2)Pd}2 (μ-OH){μ-CH2C(O)CH3}] (1) and [{(o-C6H4CH2NMe2)Pd}2 {μ-CH2C(O)CH3}2] (2). The reaction (1:2 molar ratio) of [{(AsPh3)(C6F5)Pd}2 {(μ-Cl)}2] with 20% aqueous [NBu4]OH in acetone yields [{(AsPh3)(C6F5)Pd}2 {μ-CH2C(O)CH3}2] (3). The reaction (1:1 ratio) between 2 or 3 and t-BuNC gives the monomeric complexes [(o-C6H4CH2NMe2)Pd {CH2C(O)Me}(t-BuNC)] (4) and [(AsPh3)(C6F5)Pd {CH2C(O)CH3}(t-BuNC)] (5). Heating an acetone solution of [NBu4]2 [{(C6F5)2Pd}2(μ-OH)2] gave the 2,4-dimethyl-1-oxapenta-1,3-dienyl palladium complex [NBu4][(C6F5)2Pd (η5-2,4-Me2-C4H3O)] (6). The reaction of [{(o-C6H4CH2NMe2)Pd}2 (μ-OH)2] with CH2(CO2R)2 (R = Et, Me) leads to [(o-C6H4CH2NMe2)Pd {O,O′-CH(CO2R)2}] (7, R = Me; 8, R = Et). The crystal structures of 3, 5, and 8 have been established by X-ray diffraction studies. The structure of 3 shows the C,O-enolate anion bridging two palladium atoms with a head-to-tail arrangement. In the monomeric complex 5 the C-bound acetonyl is trans to triphenylarsine. In 8 the diethyl malonate ligand and the palladium atom form a six-membered chelate ring.
