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The reaction of [Cp2 Mo2 (CO)4 (μ,η2:2 -E2 )] (A: E=P, B: E=As, Cp=C5 H5 ) with the WCA-containing CuI salts ([Cu(CH3 CN)4 ][Al{OC(CF3 )3 }4 ] (CuTEF, C), [Cu(CH3 CN)4 ][BF4 ] (D) and [Cu(CH3 CN)3.5 ][FAl{OC6 F10 (C6 F5 )}3 ] (CuFAl, E)) affords seven unprecedented coordination compounds. Depending on the E2 ligand complex, the counter anion of the copper salt and the stoichiometry, four dinuclear copper dimers and three trinuclear copper compounds are accessible. The latter complexes reveal first linear Cu3 arrays linked by E2 units (E=P, As) coordinated in an η2:1:1 coordination mode. All compounds were characterized by X-ray crystallography, NMR and IR spectroscopy, mass spectrometry and elemental analysis. To define the nature of the Cu⋅⋅⋅Cu⋅⋅⋅Cu interactions, DFT calculations were performed.

An AgI dimer capped with labile organometallic diphosphorus ligands [Cp2Mo2(CO)4(η2‐P2)] (Cp=C5H5) acts as a highly pre‐organized molecular precursor to direct the construction of 1D or 2D, and 3D organometallic–organic hybrid coordination polymers upon reaction with ditopic pyridine‐based linkers. The formation of the supramolecular aggregates can be controlled by the stoichiometry of the organic molecules, and the mechanism is supported by DFT calculations.

The three-component reaction of the tetrahedral diphosphorus complex [Cp2Mo2(CO)(4)(eta(2)-P-2)] (1), with Ag[BF4] (2) in the presence of 2,2'-bipyrimidine (3) leads to the formation of the two novel two-dimensional networks 4 and 5. Compound 4 is a new two-dimensional organometallic-organic hybrid polymer, while derivative 5 represents a unique two-dimensional organometallic-inorganic-organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two-component reactions with organic molecules in addition of metal ions.

The synthesis of the air-stable and highly soluble Cu(i)-acetonitrile salts [Cu(CH3CN)3.5][FAl] (1) ([FAl] = FAl{OC(C6F10)(C6F5)}3) and [Cu(CH3CN)4][TEF] (2) ([TEF] = Al{OC(CF3)3}4) is presented. Compound 1 reacts with the organometallic polyphosphorus complexes [Cp2Mo2(CO)4(η2-P2)] (A) and [(Cp*Fe(η5-P5)] (B) and salt 2 reacts with B to form one new (3) and three unprecedented (4-6) phosphorus-rich Cu(i) dimers with the general formulas [Cu2(μ,η1:η1-A)2(η2-A)2][FAl]2 (3), [Cu2(μ,η1:η1-A)2(η1-CH3CN)4][FAl]2 (4), [Cu2(μ,η1:η1-B)2(η1-CH3CN)4][FAl]2 (5) and [Cu2(μ,η1:η1-B)2(η1-CH3CN)4][TEF]2 (6).