Unexpected fragmentations of triphosphaferrocene – formation of supramolecular assemblies containing the (1,2,4-P₃C₂Mes₂)⁻ ligand

Abstract

While reacting the sterically demanding triphosphaferrocene [Cp*Fe(η(5)-P3C2Mes2)] () with Cu(i) halides, the sandwich complex undergoes an unprecedented fragmentation into decamethylferrocene, FeX2 (X = Cl, Br, I) and [P3C2Mes2](-) units. Subsequently, these phospholyl ligands act as versatile, negatively charged building blocks for the formation of supramolecular aggregates representing the monomeric, dimeric and polymeric (1D and 2D) coordination compounds [(P3C2Mes2)2{Cu7(CH3CN)7(μ4-X)(μ3-X)2(μ-X)}{Cu2(μ2-X)2X}{Cu(CH3CN)(μ2-X)}]2·6CH3CN (·6CH3CN: X = Cl, ·6CH3CN: X = Br), [(P3C2Mes2)2{Cu(CH3CN)}6(μ-Br)2(μ3-Br)2{Cu(CH3CN)2Br}2]·CH3CN (·CH3CN), [(P3C2Mes2)4{Cu5(CH3CN)5(μ2-Br)}{Cu(CH3CN)2CuBr2}2{Cu(CH3CN)2}]n(+)[CuBr2]n(-)·2CH3CN (·2CH3CN), [(P3C2Mes2){Cu(CH3CN)(μ-I)}4{Cu(CH3CN)3}]·0.5C7H8·2.5CH3CN (·0.5C7H8·2.5CH3CN), [(P3C2Mes2)Cu7(CH3CN)4(μ4-I)2(μ3-I)2(μ-I)2]x·2C7H8 (·2C7H8), [(P3C2Mes2){Cu(CH3CN)3}2{Cu(μ-I)}6]·0.5CH2Cl2·3CH3CN (·0.5CH2Cl2·3CH3CN) and [Cp*Fe(CH3CN)3]n(+)[(P3C2Mes2)2{Cu(CH3CN)2}{Cu(μ-I)}6]n(-)·0.6CH2Cl2 (·0.6CH2Cl2) with rather non-typical structural motifs within the large varieties of copper halide chemistry. Besides the X-ray structural analyses the obtained assemblies were also characterized in solution in which they undergo fragmentation and re-aggregation processes.

Iron Precatalysts with Bulky Tri(tert‐butyl)cyclopentadienyl Ligands for the Dehydrocoupling of Dimethylamine‐Borane

“…European Journal complex contained an average Fe-N bond length of 1.93 Å and a Cp*-Fe distance of 1.68 Å, which are similar to the analogous distances of 1.941(4) and 1.681(2) Å found for 6 53. …”

1,2,4-Triphospholyl anions – versatile building blocks for the formation of 1D, 2D and 3D assemblies

“…Furthermore, all crystal structures contain additional solvent molecules, which are discussed only in the ESI ‡ in detail. Since several coordination compounds containing 1a exist due to the fragmentation of [Cp*Fe(η 5 -P 3 C 2 Mes 2 )], 9 the question arises, if they can also be synthesized using 1a as the starting material. Indeed, with CuI two known products can be obtained.…”

“…Recently, we have reported on an unexpected fragmentation of the triphosphaferrocene [Cp*Fe(η 5 -P 3 C 2 Mes 2 )] (Cp* = η 5 -C 5 Me 5 , Mes = 2,4,6-trimethylphenyl) into [Cp*Fe] + and [P 3 C 2 Mes 2 ] – moieties, while reacting it with CuX (X = Cl, Br, I). 9 The remaining phospholyl ligands [P 3 C 2 Mes 2 ] – serve as building blocks for a variety of coordination compounds with rare or even novel structural motifs ( Fig. 2a–c ).…”

Addition of a Cyclophosphine to Nitriles: An Inorganic Click Reaction Featuring Protio, Organo, and Main‐Group Catalysis

“…There is renewed interest– in the fundamental chemistry of phosphorus heterocycles because of their potential for applications as optoelectronic materials, anion sensors, linkers in supramolecular chemistry, and metal‐free catalysts ,. As a result, the stoichiometric and catalytic additions of P−P σ bonds to alkenes, alkynes, and ketones is an area of intensive research .…”