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Mixed Organometallic–Organic Hybrid Assemblies Based on the Diarsene Complex [Cp<sub>2</sub>Mo<sub>2</sub>(CO)<sub>4</sub>(μ,η<sup>2</sup>‐As<sub>2</sub>)], Ag<sup>I</sup> Salts and N‐Donor Organic Molecules
15
Citations
74
References
2021
Year
The reaction of the organometallic diarsene complex [Cp<sub>2</sub> Mo<sub>2</sub> (CO)<sub>4</sub> (η<sup>2</sup> -As<sub>2</sub> )] (1) with Ag[Al{OC(CF<sub>3</sub> )<sub>3</sub> }<sub>4</sub> ] (Ag[TEF]) yielded the Ag<sup>I</sup> monomer [Ag(η<sup>2</sup> -1)<sub>3</sub> ][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 [{(η<sup>2</sup> -1)<sub>2</sub> Ag}<sub>2</sub> (μ-L1)][TEF]<sub>2</sub> (3) or the 1D polymer [{(η<sup>2</sup> -1)Ag}(μ-L1)]<sub>n</sub> [TEF]<sub>n</sub> (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 [{(η<sup>2</sup> -1)Ag}<sub>2</sub> (μ-Lx)<sub>3</sub> ]<sub>n</sub> [TEF]<sub>2n</sub> [Lx=L2 (5), L3 (6), L4 (7), respectively]. Additionally, this concept was extended to step-by-step one-pot reactions of 1, [Ag(CH<sub>3</sub> CN)<sub>3</sub> ][Al{OC(CF<sub>3</sub> )<sub>2</sub> (CCl<sub>3</sub> )}<sub>4</sub> ] ([Ag(CH<sub>3</sub> CN)<sub>3</sub> ][TEF<sup>Cl</sup> ]) and linkers L2-L4 to produce the 2D polymers [{(η<sup>2</sup> -1)Ag}<sub>2</sub> (μ,Lx)<sub>3</sub> ]<sub>n</sub> [TEF<sup>Cl</sup> ]<sub>2n</sub> [Lx=L2 (8), L3 (9), L4 (10), respectively].
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