SYNTHESES AND CHARACTERIZATION OF CATIONIC (TRIS(PYRAZOLYL)METHANE)SILVER(I) COMPLEXES - SOLID-STATE STRUCTURES OF ([HC(3,5-ME(2)PZ)(3)]AG-2)(O3SCF3), ([HC(3-BU(T)PZ)(3)]AG)(O3SCF3), AND ([HC(3-BU(T)PZ)(3)]AG(CNBU(T)))(O3SCF3)

Reaction of Ag(O3SCF3) with 2 equiv of HC(3,5-Me(2)pz)(3) in tkf provi des the stable six-coordinate ''sandwich'' complex {[HC(3,5-Me(2)pz)(3 )]Ag-2}(O3SCF3). The solid-state structure shows that the coordination geometry about the silver is a trigonally distorted octahedron. Subst antial tilting of the pyrazolyl rings away from alignment with the met al is observed in this six-coordinate complex, with the average AgN-NC torsion angles of the rings = 137 degrees. Reaction of equimolar amou nts of Ag(O3SCF3) and HC(3-Bu(t)pz)(3) yields {[HC(3-Bu(t)pz)(3)]Ag}(O 3SCF3). Addition of 1 molar equiv of Bu(t)NC to a CH2Cl2 solution of { [HC(3-Bu(t)pz)(3)]Ag}(O3SCF3) yields {[HC(3-Bu(t)pz)(3)]Ag(CNBu(t))}(O 3SCF3). The solid-state structures of both cations are very similar an d show pseudotetrahedral geometry about silver. An oxygen atom from th e triflate group provides the fourth donor atom in the structure of {[ HC(3-Bu(t)pz)(3)]Ag}(O3SCF3).