Au-Containing Coordination Polymers Based on Polyphosphorus Ligand Complexes.

Whereas the self-assembly of pentaphosphaferrocenes [CpRFe(η5-P5)] (CpR = Cp*, Cp×, and CpBn) 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 [CpRFe(η5-P5)] with Au salts of different anions (GaCl4-, SbF6-, and Al(OC(CF3)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.

Iodination of cyclo-E5 -Complexes (E=P, As).

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*MP6 I6 ]+ 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(CH3 CN)6 ]2+ salts of the rare [As6 I8 ]2- (in 7) and [As4 I14 ]2- (in 8) anions, the first di-cationic Fe-As triple decker complex [(Cp*Fe)2 (µ,η5:5 -As5 )][As6 I8 ] (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 )][As6 I8 ]0.5 (11) represents the first Ru-As5 triple decker complex, thus completing the series of monocationic complexes [(CpR M)2 (µ,η5:5 -E5 )]+ (M=Fe, Ru; E=P, As). [(Cp*Ru)2 As8 I6 ] (12) crystallizes as a racemic mixture of both enantiomers, while [(Cp*Ru)2 As4 I4 ] (13) crystallizes as a symmetric and an asymmetric isomer and features a unique tetramer of {AsI} arsinidene units as a middle deck.

From nano-balls to nano-bowls.

Pentaphosphaferrocene [Cp*Fe(η5-P5)] in combination with Cu(i) halides is capable of a template-directed synthesis of fullerene-like spheres. Herein, we present the use of a triple decker complex as template that leads to the formation of unprecedented 'nano-bowls'. These spherical domes resemble the truncated fullerenes I h-C80 and represent a novel spherical arrangement in the chemistry of spherical molecules.

Anionic Hosts for the Incorporation of Cationic Guests.

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}8 Cu24.25 Br28.25 (CH3 CN)6 ]4- } (4), {[Cp2 Co]+ @[{1 a}8 (CuI)28 (CH3 CN)9.8 ]}{[Cp2 Co]+ @[{1 a)}8 Cu24.4 I26.4 (CH3 CN)8 ]2- } (5), and [{1 a}3 {(1 a)2 NH}3 Cu16 I10 (CH3 CN)7 ] (6), respectively.