The Potential of the Diphosphorus Complex [Cp2W2(CO)4(η2-P2)] as an Organometallic Connecter in Supramolecular Chemistry

Abstract

For the first time, the tetrahedral diphosphorus complex [Cp2W2(CO)4(µ,η2:η2-P2)] (Cp = C5H5) (3) is used as a connecter in supramolecular chemistry. The treatment of 3 with CuI halides leads to the formation of the new one-dimensional (1D) linear polymers [Cu(µ-X){Cp2W2(CO)4(µ,η2:η2:η1:η1-P2)}]n {X = Cl (4), Br (5), I (6)}. The coordination polymers (CPs) 4–6 are almost insoluble in organic solvents, thus, their 31P 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′2W2(CO)4(µ,η2:η2-P2)] {Cp′ = C5H4{C(CH3)3}} (7) with CuBr, the unprecedented soluble 1D CP [Cu(µ-Br){Cp′2W2(CO)4(µ,η2:η2:η1:η1-P2)}]n (8) is obtained. Furthermore, the reactions of 3 with the AgI salts Ag[CF3SO3] and Ag[PF6] result in the formation of the oligomeric dicationic species [Ag2{Cp2W2(CO)4(µ,η2:η2:η2-P2)}2 {Cp2W2(CO)4(µ,η2:η2:η1:η1-P2)}2][X′]2 {X′ = [CF3SO3]– (9), [PF6]– (10)}.