Supramolecular compounds assembled from the heteroleptic tetrahedral complex [{CpMo(CO)}(μ,η-AsSb)] and metal salts.

The reaction of the tetrahedral complex [{CpMo(CO)}(μ,η-AsSb)] with Cu and Ag salts is presented which gives unprecedented neutral and cationic supramolecular aggregates featuring mixed As/Sb-donor molecules as ligands/linkers between metal ions.

Novel synthetic route towards heteroleptic pnictogen-rich organometallic-inorganic coordination compounds.

The reaction of the Ag(I) dimer [Ag(η-A)(μ,η:η-A)][TEF] (A = [{CpMo(CO)}(μ,η-P)]) possessing labile η-coordinated P ligands with the organometallic dipnictogen compounds [{CpMo(CO)}(μ,η-EE')] (E = E' = As, Sb; E = P, E' = As, Sb) represents a facile synthetic route towards unprecedented heteroleptic pnictogen-rich supramolecular complexes. This method can also be extended to the analogous Cu(I) dimer and is studied by DFT computations.

Organometallic-Organic Hybrid Assemblies Featuring the Diantimony Complex [Cp Mo (CO) (μ,η -Sb )], Ag Ions and N-Donor Molecules as Building Blocks.

The reactions of the organometallic ligand complex [Cp Mo (CO) (μ,η -Sb )] (C) with Ag[TEF] ([TEF] =[Al{OC(CF ) } ] ) in the presence of a number of di- or polytopic N-donor molecules (1,6,7,12-tetraazaperylene (L1), 2,2'-bipyrimidine (L2), 4,4'-bipyridine (L3), trans-1,2-di(4-pyridyl)ethylene (L4) and 1,3-di(4-pyridyl)propane (L5)), were studied. Depending on the reaction stoichiometry and choice of linker, these reactions lead to the selective formation of dimeric or tetrameric supramolecular coordination complexes as well as 1D and 2D coordination polymers (CPs). The presented compounds are unique examples of supramolecular complexes incorporating both organometallic Sb-donor and organic N-donor molecules as ligands to stabilize metal ions.

Diantimony Complexes [Cp Mo (CO) (μ,η -Sb )] (Cp =C H , C H Bu) as Unexpected Ligands Stabilizing Silver(I) (n=1-4) Monomers, Dimers and Chains.

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 and As (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.

Versatile Coordination of Ag and Cu Ions towards cyclo-As Ligands.

The reactions of the cyclo-As complex [Cp*Fe(η -As )] (B) with the Ag and Cu salts of the weakly coordinating anion (WCA) [FAl{OC F (C F )} ] ([FAl] ) are studied. These reactions allow the synthesis of the mononuclear complexes [M(η  : η -B) ][FAl] (M=Ag (1), Cu (2)) when a ratio of B/M(FAl) 2 : 1 is used. Compound 1 shows an unusual disorder of the central Ag cation between two π-coordinating cyclo-As ligands, which is absent in 2 pointing to a weak interaction of the Ag center towards the cyclo-As ligands in B.

Mixed Organometallic-Organic Hybrid Assemblies Based on the Diarsene Complex [Cp Mo (CO) (μ,η -As )], Ag Salts and N-Donor Organic Molecules.

The reaction of the organometallic diarsene complex [Cp Mo (CO) (η -As )] (1) with Ag[Al{OC(CF ) } ] (Ag[TEF]) yielded the Ag monomer [Ag(η -1) ][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 -1) Ag} (μ-L1)][TEF] (3) or the 1D polymer [{(η -1)Ag}(μ-L1)] [TEF] (4) depending on the ratio of the reactants.

The Potential of the Diarsene Complex [(C H ) Mo (CO) (μ,η -As )] as a Connector Between Silver Ions.

The reaction of the organometallic diarsene complex [Cp Mo (CO) (μ,η -As )] (B) (Cp = C H ) with Ag[FAl{OC F (C F )} ] (Ag[FAl]) and Ag[Al{OC(CF ) } ] (Ag[TEF]), respectively, yields three unprecedented supramolecular assemblies [(η -B) Ag ][FAl] (4), [(μ,η :η -B) (η -B) Ag ][TEF] (5) and [(μ,η :η -B) Ag ][TEF] (6). These products are only composed of the complexes B and Ag . Moreover, compounds 5 and 6 are the only supramolecular assemblies featuring B as a linking unit, and the first examples of [Ag ] units stabilized by organometallic bichelating ligands.

The Potential of the Diphosphorus Complex [CpW(CO)(η-P)] as an Organometallic Connecter in Supramolecular Chemistry.

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