The Potential of the Diphosphorus Complex [Cp(2)W(2)(CO)(4)(η(2)‐P(2))] as an Organometallic Connecter in Supramolecular Chemistry

For the first time, the tetrahedral diphosphorus complex [Cp(2)W(2)(CO)(4)(µ,η(2):η(2)‐P(2))] (Cp = C(5)H(5)) (3) is used as a connecter in supramolecular chemistry. The treatment of 3 with Cu(I) halides leads to the formation of the new one‐dimensional (1D) linear polymers [Cu(µ‐X){Cp(2)W(2)(CO)(4)(µ,η(2):η(2):η(1):η(1)‐P(2))}](n) {X = Cl (4), Br (5), I (6)}. The coordination polymers (CPs) 4–6 are almost insoluble in organic solvents, thus, their (31)P MAS‐NMR spectra were recorded and found to be remarkably influenced by their solid‐state structures. Additionally, we demonstrate that by reacting the Cp‐substituted diphosphorus complex [Cp′(2)W(2)(CO)(4)(µ,η(2):η(2)‐P(2))] {Cp′ = C(5)H(4){C(CH(3))(3)}} (7) with CuBr, the unprecedented soluble 1D CP [Cu(µ‐Br){Cp′(2)W(2)(CO)(4)(µ,η(2):η(2):η(1):η(1)‐P(2))}](n) (8) is obtained. Furthermore, the reactions of 3 with the Ag(I) salts Ag[CF(3)SO(3)] and Ag[PF(6)] result in the formation of the oligomeric dicationic species [Ag(2){Cp(2)W(2)(CO)(4)(µ,η(2):η(2):η(2)‐P(2))}(2) {Cp(2)W(2)(CO)(4)(µ,η(2):η(2):η(1):η(1)‐P(2))}(2)][X′](2) {X′ = [CF(3)SO(3)](–) (9), [PF(6)](–) (10)}.