An Icosidodecahedral Supramolecule Based on Pentaphosphaferrocene: From a Disordered Average Structure to Individual Isomers

Abstract

Pentaphosphaferrocenes [CpRFe(η5‐P5)] (1) and CuI halides are excellent building blocks for the formation of discrete supramolecules. Herein, we demonstrate the potential of Cu(CF3SO3) for the construction of the novel 2D polymer [{Cp*Fe(μ4,η5:1:1:1‐P5)}{Cu(CF3SO3)}]n (2) and the unprecedented nanosphere (CH2Cl2)1.4@[{CpBnFe(η5‐P5)}12{Cu(CF3SO3)}19.6] (3). The supramolecule 3 has a unique scaffold beyond the fullerene topology, with 20 copper atoms statistically distributed over the 30 vertices of an icosidodecahedron. Combinatorics was used to interpret the average disordered structure of the supramolecules. In this case, only two pairs of enantiomers with D5 and D2 symmetry are possible for bidentate bridging coordination of the triflate ligands. DFT calculations showed that differences in the energies of the isomers are negligible. The benzyl ligands enhance the solubility of 3, enabling NMR‐spectroscopic and mass‐spectrometric investigations.

Functionalization of Pentaphosphorus Cations by Complexation

“…[5,6] Tr ansition-metal polyphosphides such as pentamethylpentaphosphaferrocene are used as building blocks for 1D and 2D polymers and spherical supramolecules. [7,8] Alkylation, protonation, halogenation, reduction, and oxidation reactions of polyphosphorus units in neutral transition-metal complexes have been reported, [9] while the reaction of main-group-element nucleophiles such as amides,p hosphanides,h ydrocarbyl anions,a nd N-heterocyclic carbenes (NHCs) is av ersatile route to anionic complexes with functionalized polyphosphido ligands. [10] In addition, Cummins and co-workers have very impressively demonstrated the synthetic potential of polyphosphido transition metalate anions for the synthesis of useful and novel Pcompounds.…”

Au-Containing Coordination Polymers Based on Polyphosphorus Ligand Complexes

“…In combination with the group 13 metal salts M­[TEF] (M = Ga, In, and Tl; TEF = Al­(OC­(CF 3 ) 3 ) 4 ), a series of isostructural 1D polymers was obtained . When using Cu­(I) salts of halides or weakly coordinating anions (WCAs) instead, a myriad of 1D–3D coordination polymers become accessible . However, depending on the reaction conditions employed, also spherical assemblies are obtained, which partially act as hosts for smaller molecules. ,,, The application of WCAs is of special importance when aggregates with Ag cations are targeted, since Ag­(I) halides are poorly soluble.…”

Linking of CuI Units by Tetrahedral Mo2E2 Complexes (E=P, As)

“…[7] We werea blet os how the formation of 1D, 2D and even 3D coordinationp olymers, [8] organometallic-based nanosized capsules [9] and inorganic spherical supramolecules. [10] In addition to polyphosphorus complexes, organometallic polyarsenic ligand complexes have been knownf or many years. [11] However, their coordination chemistry has been ar ather unexploreda rea so far.…”