Synthesis and Characterization of Palladium(II) Complexes with New Polydentate Nitrogen Ligands. Dynamic Behavior Involving Pd-N Bond Rupture. X-ray Molecular Structure of [{Pd(eta(3)-C(4)H(7))}(2)(Me-BPzTO)](4-MeC(6)H(4)SO(3)) [Me-BPzTO = 4,6-Bis(4-methylpyrazol-1-yl)-1,3,5-triazin-2-olate].
The ligands 2,4,6-tris(4-methylpyrazol-1-yl)-1,3,5-triazine (Me-TPzT), 2,4,6-tris(4-bromopyrazol-1-yl)-1,3,5-triazine (Br-TPzT), and 2-methoxy-4,6-bis(4-methylpyrazol-1-yl)-1,3,5-triazine (Me-BPzTOMe) have been synthesized and their reactions with some palladium derivatives explored. The palladium fragment [Pd(eta(3)-2-Me-C(3)H(4))(S)(2)](+), S = acetone, reacts in acetone with Me-TPzT or Br-TPzT in a 3:1 molar ratio to generate new complexes in which two allylpalladium fragments are present and the TPzT ligands have been partially hydrolyzed: [{Pd(eta(3)-C(4)H(7))}(2)(X-BPzTO)]A, X-BPzTO = 4,6-bis[4-methyl(or bromo)pyrazol-1-yl]-1,3,5-triazin-2-olate (X = Me, A = BF(4), 1; A = PF(6), 2; A = CF(3)SO(3), 3; A = p-MeC(6)H(4)SO(3), 4; X = Br, A = CF(3)SO(3), 5). When the ligand Me-BPzTOMe is made to react with only 1 equiv of the palladium solvate, compound 6, [Pd(eta(3)-2-Me-C(3)H(4))(Me-BPzTOMe)]CF(3)SO(3), is isolated. Reaction of 6 with another 1 equiv of the palladium derivative leads to 3. The intermediate 7, [{Pd(eta(3)-2-Me-C(3)H(4))}(2)(Me-BPzTOMe)]CF(3)SO(3), has been isolated as an almost pure compound. The reaction of Me-BPzTOMe with 1 equiv of [Pd(C(6)F(5))(2)(cod)] (cod = 1,5-cyclooctadiene) leads to the complex [Pd(C(6)F(5))(2)(Me-BPzTOMe)], 8. Attention has been focused on the dynamic behavior, related with metallotropic phenomena, of the new complexes. (1)H NMR variable-temperature studies of complexes 1, 6, and 8 have been carried out. For 8, only one static species is observed, while, for 1 and 6, two isomers are detected at low temperature. Different DeltaG(c)() activation energies at the coalescence temperature have been determined and are ascribed to processes implying Pd-N bond ruptures. For 6, two different barriers are detected, corresponding to Pd-N(triazine) or Pd-N(pyrazole) bond ruptures. From the DeltaG(c)() data, it is concluded that the main driving force of the hydrolysis process is the formation of a better coordinating ligand. The molecular structure of 4 has been determined by X-ray diffraction. The meso isomer, in which the two C-Me axes of the allylic groups are oriented in the same direction, is found in the solid state.
Gómez-De La Torre
Felipe
F
Instituto de Química Médica, CSIC, Juan de la Cierva, 3, 28006-Madrid, Spain.
de La Hoz
Antonio
A
Jalón
Félix A.
FA
Manzano
Blanca R.
BR
Otero
Antonio
A
Rodríguez
Ana M.
AM
Rodríguez-Pérez
M. Carmen
MC
Echevarría
Aurea
A
Elguero
José
J