Giant Rugby Ball [{Cp^BnFe(η⁵-P₅)}₂₄Cu₉₆Br₉₆] Derived from Pentaphosphaferrocene and CuBr₂

Abstract

The self-assembly of [CpBnFe(η5-P5)] (CpBn = η5-C5(CH2Ph)5) with CuBr2 leads to the formation of an unprecedented rugby ball-shaped supramolecule consisting of 24 units of the pentaphosphaferrocene and an extended CuBr framework, which does not follow the fullerene topology. The resulting scaffold of 312 noncarbon atoms reveals three different coordination modes of the cyclo-P5 ligand including a novel π-coordination. The outer dimensions of 3.7 × 4.6 nm of the sphere approach the range of the size of proteins. With a value of 32.1 nm3, it is 62 times larger in volume than a C60 molecule. Surprisingly, this giant rugby ball is also slightly soluble in CH2Cl2.

cyclo‐P4 Building Blocks: Achieving Non‐Classical Fullerene Topology and Beyond

“…This single result led to some decisive questions as to whether the concept of structural arrangements of four‐ and six‐membered rings in supramolecules could be extended to unprecedented spherical structural motifs as it was possible for the five‐membered ring of pentaphosphaferrocene 2, 7. Moreover, further information on the formation process and the structural stability in solution was required as the insolubility of the formerly obtained 32‐vertex ball 2 a did not allow for any investigations of its behavior in solution.…”

Oxidation Chemistry of Inorganic Benzene Complexes

“…In recent decades, the evolution of E n ligand complexes( E= P, As) that are isolobal to well-known organic molecules impressively exemplifiedt he inseparability of organic and inorganic chemistry. [1][2][3] Besides their rich coordination chemistry [4] including dynamic complexes, [5] polymers, [6,7] and fullerene-like nanospheres, [8,9] our group is especially interested in the unique reactivity of these E n ligand complexes and the comparison to their organic analogs.I tw as shown that the ferrocene analogous complex [Cp*Fe(h 5 -P 5 )] readily reacts with main group nucleophiles underb ond formationa nd rearrangemento ft he planar cyclo-P 5 ligand to an envelope conformation. [10] Additionally,[ Cp*Fe(h 5 -P 5 )] exhibits ad istinctly different redox behavior than ferrocene, with single-electron oxidation as well as reduction,r esulting in dimerization through PÀPb ond formation.…”

Anionic Hosts for the Incorporation of Cationic Guests

“…This overall number of P 5 units in the sphere is exceptional because fullerene-like speciesu sually contain 12 cyclo-P 5 ligands. [4] There is only one CuBr-containing supramolecule knownw ith 24 units of 1a, [17] and anothero ne, however CuI-based, with 10 P 5 rings, possessing ac ube-like scaffold (Figure 1c). [4c] The CuBr scaffoldi n4 consists of as everely disordered middle framework with the sum composition of Cu 16.…”