title: Coordination properties of new bis(1,4,7-triazacyclononane) ligands: a highly active dizinc complex in phosphate diester hydrolysis.
abstract: The synthesis and characterization of three new bis([9]aneN(3)) ligands, containing respectively 2,2'-bipyridine (L(1)), 1,10-phenanthroline (L(2)), and quinoxaline (L(3)) moieties linking the two macrocyclic units, are reported. Proton binding and Cu(II), Zn(II), Cd(II), and Pb(II) coordination with L(1)-L(3) have been studied by potentiometric titrations and, for L(1) and L(2), by spectrophotometric UV-vis measurements in aqueous solutions. All ligands can give stable mono- and dinuclear complexes. In the case of L(1), trinuclear Cu(II) complexes are also formed. The stability constants and structural features of the formed complexes are strongly affected by the different architecture and binding properties of the spacers bridging the two [9]aneN(3) units. In the case of the L(1) and L(2) mononuclear complexes, the metal is coordinated by the three donors of one [9]aneN(3) moiety; in the [ML(2)](2+) complexes, however, the phenanthroline nitrogens are also involved in metal binding. Finally, in the [ML(3)](2+) complexes both macrocyclic units, at a short distance from each other, can be involved in metal coordination, giving rise to sandwich complexes. In the binuclear complexes each metal ion is generally coordinated by one [9]aneN(3) unit. In L(1), however, the dipyridine nitrogens can also act as a potential binding site for metals. The dinuclear complexes show a marked tendency to form mono-, di-, and, in some cases, trihydroxo species in aqueous solutions. The resulting M-OH functions may behave as nucleophiles in hydrolytic reactions. The hydrolysis rate of bis(p-nitrophenyl)phosphate (BNPP) was measured in aqueous solution at 308.1 K in the presence of the L(2) and L(3) dinuclear Zn(II) complexes. Both the L(2) complexes [Zn(2)L(2)(OH)(2)](2+) and [Zn(2)L(2)(OH)(3)](+) and the L(3) complex [Zn(2)L(3)(OH)(3)](+) promote BNPP hydrolysis. The [Zn(2)L(3)(OH)(3)](+) complex is ca. 2 orders of magnitude more active than the L(2) complexes, due both to the short distance between the metal centers in [Zn(2)L(3)(OH)(3)](+), which could allow a bridging interaction of the phosphate ester, and to the simultaneous presence of single-metal bound nucleophilic Zn-OH functions. These structural features are substantially corroborated by semiempirical PM3 calculations carried out on the mono-, di-, and trihydroxo species of the L(3) dizinc complex.
authors.affiliation: Dipartimento di Chimica Inorganica ed Analitica, Università degli Studi di Cagliari, SS 554 Bivio per Sestu, 09042 Monserrato (CA), Italy.
authors.forename: Massimiliano
authors.initials: M
authors.lastname: Arca
authors.forename: Andrea
authors.initials: A
authors.lastname: Bencini
authors.forename: Emanuela
authors.initials: E
authors.lastname: Berni
authors.forename: Claudia
authors.initials: C
authors.lastname: Caltagirone
authors.forename: Francesco A
authors.initials: FA
authors.lastname: Devillanova
authors.forename: Francesco
authors.initials: F
authors.lastname: Isaia
authors.forename: Alessandra
authors.initials: A
authors.lastname: Garau
authors.forename: Claudia
authors.initials: C
authors.lastname: Giorgi
authors.forename: Vito
authors.initials: V
authors.lastname: Lippolis
authors.forename: Alessandro
authors.initials: A
authors.lastname: Perra
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Tei
authors.forename: Barbara
authors.initials: B
authors.lastname: Valtancoli