Anionic Hosts for the Incorporation of Cationic Guests

Abstract

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.

Substituted aromatic pentaphosphole ligands – a journey across the p-block

“… 10 One of the most prominent examples of such complexes is pentaphosphaferrocene [Cp*Fe(η 5 -P 5 )] ( 1 ). 9 a While 1 readily reacts with various monovalent metal salts to form coordination compounds, 11 we could also demonstrate both its redox reactivity 12 and its behavior towards anionic 13 and neutral nucleophiles. 14 These reactions yielded complexes with bent cyclo -P 5 R ligands ( I , Scheme 1 ), 13,14 which are also accessible by the reaction of a niobium phosphorus triple bond complex with P 4 .…”

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

“…and coordination polymers [19][20][21] with the mixed σ-/π-coordination mode, which is not typical for classical ferrocene species.…”

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.…”