Metal‐Deficient Supramolecule Based on a Fivefold‐Symmetric Building Block

Abstract

An unprecedented cationic supramolecule [(Cp′′Fe(η 5 ‐P 5 )) 12 {CuNCMe} 8 ] 8+ 2.66 nm in diameter was selectively isolated as a salt of the weakly coordinating anion [Al{OC(CF 3 ) 3 } 4 ] − for the first time and characterized by X‐ray structure analysis, PXRD, NMR spectroscopy, and mass spectrometry. Its metal‐deficient core contains the lowest possible number of Cu atoms to connect 12 pentaphosphaferrocene units, providing a supramolecule with fullerene topology which, topologically, also represents the simplest homologue in the family of metal‐deficient pentaphosphaferrocene‐based supramolecules [{Cp R Fe(η 5 ‐P 5 )} 12 (CuX) 20− n ]. The 12 vacant metal sites between the cyclo‐P 5 rings, the largest number attained to date, make this compound a facile precursor for potential inner and outer modifications of the core as well as for functionalization via the substitution of labile acetonitrile ligands.

Structural Chemistry of Giant Metal Based Supramolecules

“…This phenomenon has been studied more systematically for a so-called 80-vertex pentaphosphaferrocene-based supramolecules possessing a highly symmetric scaffold (Figure and Table ). − In the idealized case, 12 cyclo -P 5 rings of the [Cp R Fe­(η 5 -P 5 )] organometallic building blocks coordinate 20 CuHal units (Hal = Cl, Br, and I) resulting in the {Cu 20 P 80 } core of fullerene-C 80 topology possessing icosahedral I h symmetry and containing a total of 20 copper and 60 phosphorus atoms in the core. The 20 copper atoms form a pentagon-icosahedral arrangement.…”

“…(a, b) 80-vertex supramolecules built up from Cp*Fe­(η 5 -P 5 ) and Cp Bn Fe­(η 5 -P 5 ) building blocks; (c) complete, 1-Cu and one of the isomers of 2-Cu-deficient Cu/P/Hal core; ,, (d, e) [(Cp″Fe­(η 5 -P 5 )) 12 (CuCH 3 CN) 8 ] 8+ and 12-Cu-deficient core with silver cycles depicting the missing Cu sites . H atoms and guest molecules are omitted for clarity.…”

“…Using [Al(OC(CF 3 ) 3 ) 4 ] − (teflonate) as such a WCA anion, we obtained a compound containing the cationic supramolecule [(Cp″Fe(η 5 -P 5 )) 12 (CuCH 3 CN) 8 ] 8+ (Cp″ = η 5 -1,3-t Bu-C 5 H 3 ) with a 12-copper-deficient core {Cu 20−12 (Cp″Fe-(η 5 -P 5 )) 12 } that is perfectly ordered in the crystal (Figure 63d,e and Table 11). 343 Not only a single metal cation but also a polymetallic fragment in the MOC can be absent, 11 and Figure 64b). 264 These supramolecules can be described as the result of the formal removal of the {Co 4 (BTC4A)} fragment from the related octahedral closed-cage MOCs {Co 24 (BTC4A) 6 } (Figure 64a).…”

The Missing Parent Compound [(C5H5)Fe(η5‐P5)]: Synthesis, Characterization, Coordination Behavior and Encapsulation

“…The only example of as upramolecule based on a1 ,3-coordinationm ode of [Cp''Fe(h 5 -P 5 )] with-interestingly,aminimum amount of metal cations-has been obtained only very recently. [30] In contrast, 3 forms twodimensional layers.W hen the bridging iodine atoms andt he 1,3-coordinated 1b molecules are treated as spacers and the Cu atoms as nodes of thep olymerics tructure, the honeycomb hcb topology of the layer becomes evident. [29,31] Compound 4 crystallizesa sr ed prisms in the orthorhombic space group Pna2 1 .R emarkably,i ti saconstitutional isomer of 3,h aving the same sum formula [{CpFe(h 5 -P 5 )}Cu(m-I)] n but different connectivity,r epresenting the first example of a3 Dp entaphosphaferrocene-based polymer.T his is astonishing, since all obtained pentaphosphaferrocene-based polymers are either 1D or 2D.…”

Synthesis of 3,4,5-tris(chlorophenyl)-1,2-diphosphaferrocenes and their electrochemical properties

“…Recently, pentaphosphaferrocene [Cp*Fe(η 5 -P5)] has been used as a mediator in the synthesis of asymmetric phosphines starting from white phosphorus [15]. Moreover, the presence of P-atom's lone pair opens the route to polynuclear complexes [16,17,18] and coordination polymers [19,20,21] with the mixed σ/π coordination mode, which is not typical for classical ferrocene species.…”