Structural Comparisons of Silver(I) Complexes of Third-Generation Ligands Built from Tridentate (<i>o</i>-C<sub>6</sub>H<sub>4</sub>[CH<sub>2</sub>OCH<sub>2</sub>C(pz)<sub>3</sub>]<sub>2</sub>) versus Bidentate Poly(1-pyrazolyl)methane Units (<i>o</i>-C<sub>6</sub>H<sub>4</sub>[CH<sub>2</sub>OCH<sub>2</sub>CH(pz)<sub>2</sub>]<sub>2</sub>) (pz = Pyrazolyl Ring)
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The new bitopic, bis(1-pyrazolyl)methane-based ligand o-C6H4[CH2OCH2CH(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 α,α‘-dibromo-o-xylene. The reaction of L2 with AgPF6 or AgO3SCF3 yields {o-C6H4[CH2OCH2CH(pz)2]2(AgPF6)}n or {o-C6H4[CH2OCH2CH(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-C6H4[CH2OCH2C(pz)3]2 (L3), reacts with AgO3SCF3 to form a similar coordination polymer, {o-C6H4[CH2OCH2C(pz)3]2(AgO3SCF3)}n. In this case, each tris(pyrazolyl)methane unit in L3 adopts the κ2−κ0 bonding mode. Crystallization of a 3:1 mixture of AgO3SCF3 and L3 yields {o-C6H4[CH2OCH2C(pz)3]2(AgO3SCF3)2}n, in which the tris(1-pyrazolyl)methane units adopt a κ2−κ1 coordination mode.
