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]

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Die Synthese und Reaktivität von Übergangsmetallverbindungen mit "nackten" Pnictogenatomen ist ein aktueller Forschungsgegenstand mit außergewöhnlichen Bindungsmustern in den erhaltenen Produkten. Innerhalb dieses Gebietes ist insbesondere das Koordinationsverhalten von Komplexen mit P n -und As n -(2 � n � 5) Einheiten Gegenstand intensiver Forschungen. Untersuchungen zu den schwereren Homologen wurden bisher kaum durchgeführt, da geringe Ausbeuten und eine nur mäßige Luftstabilität hohe Hürden darstellen. Nunmehr legen wir eine erste grundlegende Studie vor, die die Reaktivität metallorganischer Komplexe mit Sb-Donoratomen gegenüber verschiedenen Ag I -Salzen adressiert. Diese Reaktionen führten zu 12 neuartigen Verbindungen als Monomere, Dimere sowie drei-und viergliedrige Ketten aus Ag I -Ionen, die in der Literatur bisher als unzugänglich galten. Interatomare Abstände sowie computergestützte Belege, die mit Hilfe verschiedener Methoden erhalten wurden, weisen auf Ag•••Ag-Wechselwirkungen in allen Komplexen hin, die mehr als ein Ag I -Ion enthalten.

The first supramolecular assemblies composed of the organometallic diantimony complex [(Cp)2Mo2(CO)4(μ,η2‐Sb2)], AgI ions and various N‐donor molecules are presented; the cover feature depicts the synthesis of these organometallic–organic aggregates as a fascinating, yet challenging, adventure. The crossroads in the middle reflects the dependency of the final product's structure and dimensionality (0D, 1D, or even 2D) on N‐donor ligand choice and highlights the importance of fine tuning of the reaction conditions. More information can be found in the Research Article by M. Scheer and co‐workers (DOI: 10.1002/chem.202300610).