| Popis: |
Two series of sterically demanding para-dimethoxyphenyl-substituted bis(pyrazol-1-yl)methane ligands have been synthesized, i.e., L2(R,R') = ((MeO)(2)C(6)H(3))C(H)(pz(R,R'))(2) and L3(R,R') = ((MeO)(2)C(6)H(3))C(Me)(pz(R,R'))(2) (R,R' = 3-Me,5-Me; 3-Ph,5-H; 3-tBu,5-H). In the solid state, already the sterically least encumbered derivative L2(Me2) is able to stabilize Co(II) complexes of the form [X(2)Co(L2(Me2))] (X = Cl, NO(3)); in solution, these complexes are at an equilibrium with the 1:2 species [Co(L2(Me2))(2)](2+). Oxidative demethylation of L3(Ph) and L3((t)Bu) with [Ce(NH(4))(2)(NO(3))(6)] leads to the corresponding para-benzoquinonyl-substituted bis(pyrazol-1-yl)methane ligands L4(Ph) and L4((t)Bu). Contrary to that, the methyl derivative L3(Me2) is transformed into the ortho-benzoquinone species L5(Me2), which still contains one methoxy substituent while one oxygen atom has been newly introduced. The formation of L5(Me2) requires (i) the admission of air, (ii) the presence of both methoxy substituents of L3(Me2), and (iii) the presence of (methyl) substituents both at the exocyclic carbon atom and at the 5- positions of the pyrazolyl rings. The parent ortho-hydroquinonyl-substituted bis(pyrazol-1-yl)methane ligand ((HO)(2)C(6)H(3))C(H)(pz(H,H))(2) is readily available from 3,4-dihydroxybenzaldehyde and (pz(H,H))(2)SO/pyridine. |
