Tuning the dimensionality of organometallic-organic hybrid polymers assembled from [Cp₂Mo₂(CO)₄(η²-P₂)], bipyridyl linkers and Ag^I ions

The reactions of the P₂ ligand complex [Cp₂Mo₂(CO)₄(η²-P₂)] (Cp = C₅H₅, 1) with Ag[Al{OC(CF₃)₃}₄] (Ag[TEF]) in the presence of the rigid bipyridyl linkers 1,2-di(pyridin-4-yl)ethyne (3), 4,4′-bis(pyridin-4-ylethynyl)-1,1′-biphenyl (4) and 4,4′-bipyridine (5) possessing various lengths are studied. The reaction with the longer linkers (3 and 4) leads to the formation of the 1D organometallic-organic hybrid polymers [{Cp₂Mo₂(CO)₄(μ₄,η^1:1:2:2-P₂)}₂{Cp₂Mo₂(CO)₄(μ₃,η^1:2:2-P₂)}₂(μ,η^1:1-C₁₂H₈N₂)Ag₂]_n[TEF]_2n (6) and [{Cp₂Mo₂(CO)₄(μ₄,η^1:1:2:2-P₂)}₂{Cp₂Mo₂(CO)₄(μ₃,η^1:2:2-P₂)}₂(μ,η^1:1-C₂₆H₁₆N₂)Ag₂]_n[TEF]_2n (7) in high selectivity. A similar reaction with the short linker 5 affords a mixture of the 2D hybrid polymers [{Cp₂Mo₂(CO)₄(μ₄,η^1:2:2:2-P₂)}₂(μ,η^1:1-C₁₃H₁₄N₂)Ag₂]_n[TEF]_2n (8) and the 3D hybrid network [{Cp₂Mo₂(CO)₄(μ₄,η^1:1:2:2-P₂)}₂(μ,η^1:1-C₁₀H₈N₂)Ag]_n[TEF]_2n (9). However, a selective synthesis of 8 or 9 is possible when the reaction is performed at 0 °C and 60 °C, respectively.