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Reger DL, Foley EA, Smith MD: Mononuclear metallacyclic silver (I) complexes of third generation bis (1-pyrazolyl) methane ligands. Inorg Chem. 2009 Feb 2;48(3):936-45.
The third-generation bis (1-pyrazolyl) methane ligands p-C (6) H (4)[CH (2) OCH (2) CH (pz)(2)](2) (L (p), pz = pyrazolyl ring) and m-C (6) H (4)[CH (2) OCH (2) CH (pz)(2)](2) (L (m)) have been synthesized by the reaction of (pz)(2) CHCH (2) OH with NaH followed by alpha,alpha'-dibromo-p-xylene or alpha,alpha'-dibromo-m-xylene. The reaction of L (p) with AgBF (4), AgPF (6), and AgO (3) SCF (3) yields the new compounds {Ag [p-C (6) H (4)(CH (2) OCH (2) CH (pz)(2))(2)]}BF (4), {Ag [p-C (6) H (4)(CH (2) OCH (2) CH (pz)(2))(2)]}PF (6), and {Ag [p-C (6) H (4)(CH (2) OCH (2) CH (pz)(2))(2)]}O (3) SCF (3), respectively. A similar reaction of L (m) with AgBF (4) and AgPF (6) yields {Ag [m-C (6) H (4)(CH (2) OCH (2) CH (pz)(2))(2)]}BF (4) and {Ag [m-C (6) H (4)(CH (2) OCH (2) CH (pz)(2))(2)]}PF (6). These compounds were crystallized from both acetone and acetonitrile to yield nine crystalline forms of (LAg)(+) that differ in counterion and solvent of crystallization. In all complexes, the four pyrazolyl rings of the ligand chelate a single silver (I) cation in a distorted tetrahedral environment to form mononuclear metallacycles. This arrangement has not previously been observed with the analogous ligands based on tris (1-pyrazolyl) methane units and is unique because of the ring sizes (16-member rings in L (m) and 17-member rings in L (p)). The dominant feature in all of these solid state structures, regardless of solvent or anion, is this cationic metallacyclic architecture, which does not readily lend itself to strong supramolecular organization. |
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