Unexpected fragmentations of triphosphaferrocene - formation of supramolecular assemblies containing the (1,2,4-P(3)C(2)Mes(2))(-) ligand

作者：Heindl Claudia; Kuntz Andrea; Peresypkina Eugenia V; Virovets Alexander V; Zabel Manfred; Luedeker David; Brunklaus Gunther; Scheer Manfred^*

来源：Dalton Transactions, 2015, 44(14): 6502-6509.

DOI：10.1039/c5dt00303b

While reacting the sterically demanding triphosphaferrocene [(CpFe)-Fe-star(eta(5)-P(3)C(2)Mes(2))] (1) with Cu(I) halides, the sandwich complex undergoes an unprecedented fragmentation into decamethylferrocene, FeX2 (X = Cl, Br, I) and [P(3)C(2)Mes(2)](-) 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 [(P(3)C(2)Mes(2))(2){Cu-7(CH3CN)(7)(mu(4)-X)(mu(3)-X)(2)(mu-X)}{Cu-2(mu(2)-X)(2)X}{Cu(CH3CN)(mu(2)-X)}] (2)center dot 6CH(3)CN (2 center dot 6CH(3)CN: X = Cl, 3 center dot 6CH(3)CN: X = Br), [(P(3)C(2)Mes(2))(2){Cu-(CH3CN)}(6)(mu-Br)(2)(mu(3)-Br)(2){Cu(CH3CN)(2)Br}(2)]center dot CH3CN (4a center dot CH3CN), [(P(3)C(2)Mes(2))(4){Cu-5(CH3CN)(5)(mu(2)-Br)}{Cu(CH3CN)(2)CuBr2}(2){Cu(CH3CN)(2)}](n)(+)[CuBr2](n)(-)center dot 2CH(3)CN (5 center dot 2CH(3)CN), [(P(3)C(2)Mes(2)){Cu-(CH3CN)(mu-I)}(4){Cu(CH3CN)(3)}]center dot 0.5C(7)H(8)center dot 2.5CH(3)CN (6 center dot 0.5C(7)H(8)center dot 2.5CH(3)CN), [(P(3)C(2)Mes(2))Cu-7(CH3CN)(4)(mu(4)-I)(2)(mu(3)-I)(2)(mu-I)(2)](x)center dot 2C(7)H(8)(7 center dot 2C(7)H(8)), [(P(3)C(2)Mes(2)){Cu(CH3CN)(3)}(2){Cu(mu-I)}(6)]center dot 0.5CH(2)Cl(2)center dot 3CH(3)CN (8 center dot 0.5CH(2)Cl(2)center dot 3CH(3)CN) and [(CpFe)-Fe-star(CH3CN)(3)](n)(+)[(P(3)C(2)Mes(2))(2){Cu(CH3CN)(2)}{Cu(mu-I)} 6](n)(-)center dot 0.6CH(2)Cl(2) (9 center dot 0.6CH(2)Cl(2)) 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.

• 出版日期2015