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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,η1:1:2:2-P2)}2{Cp2Mo2(CO)4(μ3,η1:2:2-P2)}2(μ,η1:1-C12H8N2)Ag2]n[TEF]2n (6) and [{Cp2Mo2(CO)4(μ4,η1:1:2:2-P2)}2{Cp2Mo2(CO)4(μ3,η1:2:2-P2)}2(μ,η1:1-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,η1:2:2:2-P2)}2(μ,η1:1-C13H14N2)Ag2]n[TEF]2n (8) and the 3D hybrid network [{Cp2Mo2(CO)4(μ4,η1:1:2:2-P2)}2(μ,η1:1-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.

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