Synthesis and reactivity of novel cyclometallated complexes derived from [C,N,O] terdentate ligands. Crystal structure of [Pd{2,3,4-(MeO)3C6HC(H)N[2-(O)C6H4]}(PPh3)]
2002; Royal Society of Chemistry; Volume: 26; Issue: 4 Linguagem: Inglês
10.1039/b110197h
ISSN1369-9261
AutoresAlberto Fernández, D. Vázquez-García, Jesús J. Fernández, M. López-Torres, Antonio Suárez, S. Castro-Juiz, J.M. Vila,
Tópico(s)Catalytic Alkyne Reactions
ResumoTreatment of the Schiff base ligands 2,3,4-(MeO)3C6H2C(H)N[2-(OH)C6H4], a, and 2,3,4-(MeO)3C6H2C(H)N[2-(OH)-4-MeC6H4], b, with palladium(II) acetate in toluene gave the cyclometallated complexes [Pd{2,3,4-(MeO)3C6HC(H)N[2-(O)C6H4]}]n, 1a, and [Pd{2,3,4-(MeO)3C6HC(H)N[2-(O)-4-MeC6H4]}]n, 1b, respectively, as air stable solids, with the [C,N,O] ligand terdentate after deprotonation of the –OH group. Reaction of the cyclometallated complexes with triphenylphosphine gave the mononuclear species [Pd{2,3,4-(MeO)3C6HC(H)N[2-(O)C6H4]}(PPh3)], 2a, and [Pd{2,3,4-(MeO)3C6HC(H)N[2-(O)-4-MeC6H4]}(PPh3)], 2b, with cleavage of the polynuclear structure. The molecular structure of 2a has been determined by X-ray crystallography. Treatment of 1a and 1b with the diphosphines dppm, dppp, dppb, dpppe and dppf in a 1∶2 molar ratio afforded the dinuclear cyclometallated complexes [(Pd{2,3,4-(MeO)3C6HC(H)N[2-(O)C6H4]})2{μ-PPh2(CH2)nPPh2}] (3a: n = 1; 4a: n = 3; 5a: n = 4; 6a: n = 5), [(Pd{2,3,4-(MeO)3C6HC(H)N[2-(O)C6H4]})2(μ-PPh2C5H4FeC5H4PPh2)], 7a, [(Pd{2,3,4-(MeO)3C6HC(H)N[2-(O)-4-MeC6H4]})2{μ-PPh2(CH2)nPPh2}] (3b: n = 3; 4b: n = 4) and [(Pd{2,3,4-(MeO)3C6HC(H)N[2-(O)-4-MeC6H4]})2(μ-PPh2C5H4FeC5H4PPh2)], 5b, as air stable solids. Treatment of 1a and 1b with an excess of mono- or diphosphine did not produce cleavage of the Pd–Ochelating bond.
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