Depending on the reaction conditions, either guest or host truncation is observed upon self-assembly of [Cp*Fe(η5-P5)], [(CpCr)2(η5-As5)] and copper halides.

In a high‐yield one‐pot synthesis, the reactions of [Cp*M(η5‐P5)] (M=Fe (1), Ru (2)) with I2 resulted in the selective formation of [Cp*MP6I6]+ salts (3, 4). The products comprise unprecedented all‐cis tripodal triphosphino‐cyclotriphosphine ligands. The iodination of [Cp*Fe(η5‐As5)] (6) gave, in addition to [Fe(CH3CN)6]2+ salts of the rare [As6I8]2− (in 7) and [As4I14]2− (in 8) anions, the first di‐cationic Fe‐As triple decker complex [(Cp*Fe)2(μ,η5:5‐As5)][As6I8] (9). In contrast, the iodination of [Cp*Ru(η5‐As5)] (10) did not result in the full cleavage of the M−As bonds. Instead, a number of dinuclear complexes were obtained: [(Cp*Ru)2(μ,η5:5‐As5)][As6I8]0.5 (11) represents the first Ru‐As5 triple decker complex, thus completing the series of monocationic complexes [(CpRM)2(μ,η5:5‐E5)]+ (M=Fe, Ru; E=P, As). [(Cp*Ru)2As8I6] (12) crystallizes as a racemic mixture of both enantiomers, while [(Cp*Ru)2As4I4] (13) crystallizes as a symmetric and an asymmetric isomer and features a unique tetramer of {AsI} arsinidene units as a middle deck.

Whereas the self-assembly of pentaphosphaferrocenes [Cp R Fe(η 5 -P 5 )] (Cp R = Cp*, Cp × , and Cp Bn ) with Cu and Ag salts has been well-studied in the past, the coordination chemistry toward Au complexes has been left untouched so far. Herein, the results of the self-assembly processes of [Cp R Fe(η 5 -P 5 )] with Au salts of different anions (GaCl 4 − , SbF 6 − , and Al(OC(CF 3 ) 3 ) 4 (TEF − )) are reported. Next to a variety of molecular coordination products, the first coordination polymers based on polyphosphorus ligand complexes and Au salts are also obtained. Thereby, a 2D coordination polymer comprising metal vacancies is isolated. In all products, the Au centers are coordinated in a linear or a trigonal planar environment. In solution, highly dynamic processes are observed. Variable-temperature NMR spectroscopy, solid-state NMR spectroscopy, and X-ray powder diffraction were applied to gain further insight into selected coordination compounds.

Pentaphosphaferrocene [Cp*Fe(η5‐P5)] (1 a) represents an excellent building block for the template‐directed synthesis of spherical supramolecules. Here, the self‐assembly of 1 a with CuI and CuII halides in the presence of the template complexes [FeCp2][PF6], [CoCp2][PF6] and [CoCp2] is reported, testifying to the redox behavior of the formed supramolecules. The oxidation or reduction capacity of these reactive complexes does not inhibit their template impact and, for the first time, the cationic metallocene [CoCp2]+ is enclosed in unprecedented anionic organometallic hosts. Furthermore, the large variety of structural motifs, as icosahedral, trigonal antiprismatic, cuboidal and tetragonal antiprismatic arrangements of 1 a units are realized in the supramolecules [FeCp2]@[{1 a}12(CuBr)17.3] (3), [CoCp2]+ 3{[CoCp2]+@[{1 a}8Cu24.25Br28.25(CH3CN)6]4−} (4), {[Cp2Co]+@[{1 a}8(CuI)28 (CH3CN)9.8]}{[Cp2Co]+@[{1 a)}8Cu24.4I26.4(CH3CN)8]2−} (5), and [{1 a}3{(1 a)2NH}3Cu16I10(CH3CN)7] (6), respectively.