Structural comparisons of silver(I) complexes of third-generation ligands built from tridentate (o-C(6)H(4)[CH(2)OCH(2)C(pz)(3)](2)) versus bidentate poly(1-pyrazolyl)methane units (o-C(6)H(4)[CH(2)OCH(2)CH(pz)(2)](2)) (pz = pyrazolyl ring)

The new bitopic, bis(1-pyrazolyl)methane-based ligand o-C6H4CH2OCH2CH(pz)2]2 (L2, pz = pyrazolyl ring) is prepared from the reaction of (pz)2CHCH2OH (obtained from the reduction of (pz)2CHCOOH with BH3.S(CH3)2) with NaH, followed by the addition of alpha,alpha'-dibromo-o-xylene. The reaction of L2 with AgPF6 or AgO3SCF3 yields {o-C6H4CH2OCH2CH(pz)2]2(AgPF6)}n or {o-C6H4CH2OCH2CH(pz)2]2(AgO3SCF3)}n, respectively. Both compounds in the solid state have tetrahedral silver(I) centers arranged in a 1D coordination polymer network. The analogous ligand based on tris(1-pyrazolyl)methane units, o-C6H4CH2OCH2C(pz)3]2 (L3), reacts with AgO3SCF3 to form a similar coordination polymer, {o-C6H4CH2OCH2C(pz)3]2(AgO3SCF3)}n. In this case, each tris(pyrazolyl)methane unit in L3 adopts the kappa2-kappa0 bonding mode. Crystallization of a 3:1 mixture of AgO3SCF3 and L3 yields {o-C6H4CH2OCH2C(pz)3]2(AgO3SCF3)2}n, in which the tris(1-pyrazolyl)methane units adopt a kappa2-kappa1 coordination mode.