Novel Two- and Three-Dimensional Organometallic-Organic Hybrid Materials Based on Polyphosphorus Complexes

The reaction of the silver salt Ag[Al{OC(CF3)(3)}(4)] (1) with the P-2 ligand complex [Cp2Mo2(CO)(4)(eta(2)-P-2)] (2) and the organic ditopic linker trans-1,2-di(pyridine-4-yl)ethene (dpe) results in the formation of four novel organometallic-organic hybrid compounds. Depending on the reaction conditions, the two-dimensional networks [{Cp2Mo2(CO)(4)(mu(4),eta(1:1:2:2)-P-2)}(mu,eta(1:1)-C12H10N2)Ag](n)[Al{OC(CF3)(3)}(4)](n) center dot 0.075nCH(2)Cl(2) center dot 1.425nC(6)H(6) (3) and [{Cp2Mo2(CO)(4)(mu(3),eta(2:2:2)-P-2)}(2)(mu,eta(1:1)-C12H10N2)(3)Ag-2](n)[Al{OC(CF3)(3)}(4)](2n) center dot 2nC(7)H(8) (4) are accessible. The latter shows a two-dimensional (2D) -> 2D interpenetration structure. Furthermore, the formation of a unique three-dimensional polymer [{Cp2Mo2(CO)(4)(mu(4),eta(1:1:2:2)-P-2)}(mu,eta(1:1) C12H10N2)Ag](n)[Al{OC(CF3)(3)}(4)](n) center dot 0.3nCH(2)Cl(2) (5b) together with another 2D polymer [{Cp2Mo2(CO)(4)(mu(4),eta(1:1:2:2)-P-2)}(mu,eta(1:1)-C12H10N2)(3)Ag-2](n)[Al{OC(CF3)(3)}(4)](2n) center dot 0.75CH(2)Cl(2) center dot 0.5C(7)H(8) (5a) was observed. In three of these polymers, unprecedented organometallic nodes were realized including one, two, or even four silver cations. All products were characterized by X-ray structural analysis and classified by the structural characteristics in three different network topologies.