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].

The reactiono ft he organometallic diarsene complex [Cp 2 Mo 2 (CO) 4 (m,h 2-As 2)] (B)(Cp = C 5 H 5)w ith Ag[FAl{OC 6 F 10 (C 6 F 5)} 3 ](Ag[FAl]) and Ag[Al{OC(CF 3) 3 } 4 ] (Ag[TEF]), respectively,y ields three unprecedenteds upramolecular assemblies [(h 2-B) 4 Ag 2 ][FAl] 2 (4), [(m,h 1 :h 2-B) 3 (h 2-B) 2 Ag 3 ][TEF] 3 (5)a nd [(m,h 1 :h 2-B) 4 Ag 3 ][TEF] 3 (6). These products are only composed of the complexes B andA g I. Moreover,c ompounds 5 and 6 are the only supramolecular assemblies featuring B as al inking unit, and the first examples of [Ag I ] 3 units stabilized by organometallic bichelating ligands. According to DFT calculations, complex B coordinatest om etal centers through both the As lone pair and the AsÀAs s-bond thus showing this unique feature of this diarsene ligand.

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Synthesis and reactivity of transition metal compounds bearing "naked" pnictogen atoms is an active research area with remarkable bonding patterns observed in the formed compounds. Within this field, intense investigations on the coordination behavior of complexes possessing P n and As n (2 � n � 5) moieties have been conducted. However, studies on heavier analogues have been ignored so far due to arduous challenges related to low yields and moderate air stability. Herein, we present the first in-depth study addressing the reactivity of organometallic complexes containing Sb-donor atoms with several Ag I salts. These reactions afforded twelve unprecedented aggregates as monomers, dimers as well as three-and four-membered chains of Ag I ions claimed in the literature to be inaccessible. Interatomic distances as well as computational evidence obtained with help of several different methods suggest the presence of Ag•••Ag interactions in all complexes containing more than one Ag I ion.

For the first time, the tetrahedral diphosphorus complex [Cp 2 W 2 (CO) 4 (μ,η 2 :η 2 -P 2 )] (Cp = C 5 H 5 ) (3) is used as a connecter in supramolecular chemistry. The treatment of 3 with Cu I halides leads to the formation of the new one-dimensional (1D) linear polymers [Cu(μ-X){Cp 2 W 2 (CO) 4 (μ,η 2 :η 2 :η 1 :η 1 -P 2 )}] n {X = Cl (4), Br (5), I (6)}. The coordination polymers (CPs) 4-6 are almost insoluble in organic solvents, thus, their 31 P MAS-NMR spectra were recorded and found to be remarkably influenced by their solid-state structures. Additionally, we demonstrate that by re- [a]