Pyrazolato-bridged polynuclear palladium and platinum complexes. Synthesis,structure, and reactivity

Cyclic trinuclear complexes Pd(3)(mu-pz)(6)] (1) and Pd(3)(mu-4-Mepz)(6)] (2) and dinuclear complex Pd(2)(mu-3-t-Bupz)(2)(3-t-Bupz)(2)(3-t-BupzH)(2)] (3) have been prepared by the reactions of PdCl(2)(CH(3)CN)(2)] with pyrazole (pzH), 4-methylpyrazole (4-MepzH), and 3-tert-butylpyrazole (3-t-BupzH), respectively, in CH(3)CN in the presence of Et(3)N. In the absence of the base, treatment of PdCl(2)(CH(3)CN)(2)] with pzH gave the mononuclear complex, Pd(pzH)(4)]Cl(2) (6). The reaction of PtCl(2)(C(2)H(5)CN)(2)] with pzH in the presence of Et(3)N under refluxing in C(2)H(5)CN afforded the known dimeric Pt(II) complex, Pt(pz)(2)(pzH)(2)](2) (7). The protons participating in the hydrogen bonding in 3 and 7 are easily replaced by silver ions to give the heterotetranuclear complex Pd(2)Ag(2)(mu-3-t-Bupz)(6)] (4) and the heterohexanuclear complex Pt(2)Ag(4)(mu-pz)(8)] (5). The complexes 1-6 are structurally characterized.