Mixed Organometallic–Organic Hybrid Assemblies Based on the Diarsene Complex [Cp2Mo2(CO)4(μ,η2-As2)], AgI Salts and N-Donor Organic Molecules

Abstract

The reaction of the organometallic diarsene complex [Cp2Mo2(CO)4(η2-As2)] (1) with Ag[Al{OC(CF3)3}4] (Ag[TEF]) yielded the AgI monomer [Ag(η2-1)3][TEF] (2). This compound exhibits dynamic behavior in solution, which allows directed selective synthesis of unprecedented organometallic–organic hybrid assemblies upon its reaction with N-donor organic molecules by a stepwise pathway, which is supported by DFT calculations. Accordingly, the reaction of 2 with 2,2′-bipyrimidine (L1) yielded the dicationic molecular compound [{(η2-1)2Ag}2(μ-L1)][TEF]2 (3) or the 1D polymer [{(η2-1)Ag}(μ-L1)]n[TEF]n (4) depending on the ratio of the reactants. However, its reactions with the pyridine-based linkers 4,4′-bipyridine (L2), 1,2-bis(4-pyridyl)ethylene (L3) and 1,2-bis(4-pyridyl)ethyne (L4) allowed the formation of the 2D polymers [{(η2-1)Ag}2(μ-Lx)3]n[TEF]2n [Lx=L2 (5), L3 (6), L4 (7), respectively]. Additionally, this concept was extended to step-by-step one-pot reactions of 1, [Ag(CH3CN)3][Al{OC(CF3)2(CCl3)}4] ([Ag(CH3CN)3][TEFCl]) and linkers L2–L4 to produce the 2D polymers [{(η2-1)Ag}2(μ,Lx)3]n[TEFCl]2n [Lx=L2 (8), L3 (9), L4 (10), respectively].