Synthesis, characterization, crystal structure and preliminary reactivity behaviour of new heteropolytopic ligands based on the 1,3,5-triazine spacer and pyrazolyl, tris-pyrazolylmethyl and tris-pyrazolylethoxy bonding fragments

Four new potentially polytopic nitrogen donor ligands based on the 1,3,5-triazine fragment, L 1-L 4 (L 1 = 2-chloro-4,6-di(1H-pyrazol-1-yl)-1,3,5-triazine, L 2 = N,N′-bis(4,6-di(1H-pyrazol-1-yl)-1,3,5-triazin-2-yl)ethane-1,2-diamine, L 3 = 2,4,6-tris(tri(1H-pyrazol-1-yl)methyl)-1,3,5-triazine, and L 4 = 2,4,6-tris(2,2,2-tri(1H-pyrazol-1-yl)ethoxy)-1,3,5-triazine) have been synthesized and characterized. The X-ray crystal structure of L 3 confirms that its molecular nature consists of a 1,3,5-triazine ring bearing three tripodal tris(pyrazolyl) arms. L 1, L 2, and L 4 react with Cu I, Cu II, Pd II and Ag I salts yielding mono-, di-, and oligonuclear derivatives: [Cu(L 1)(Cy 3P)]ClO 4, [{Ag 2(L 2)}(CF 3SO 3) 2]·H 2O, [Cu 2(L 2)(NO 3) 2](NO 3) 2·H 2O, [Cu 2(L 2)(CH 3COO) 2](CH 3COO) 2·3H 2O, [Pd 2(L 2)(Cl) 4]·2H 2O, [Ru(L 2)(Cl)(OH)]·CH 3OH, [Ag 3(L 4) 2](CF 3SO 3) 3 and [Ag 3(L 4) 2](BF 4) 3. The interaction of L 3 with Ag I, Cu II, Zn II and Ru II complexes unexpectedly produced the hydrolysis of the ligand with formation, in all cases, of tris(pyrazolyl)methane (TPM) derivatives. In detail, the already known [Ag(TPM) 2](CF 3SO 3) and [Cu(TPM) 2](NO 3) 2, as well as the new [Zn(TPM) 2](CF 3SO 3) 2 and [Ru(TMP)(p-cymene)] Cl(OH)·2H 2O complexes have been isolated. Single-crystal XRD determinations on the latter derivatives confirm their formulation, evidencing, for the Ru II complex, an interesting supramolecular arrangement of the anions and crystallization water molecules.