A General Pathway to Heterobimetallic Triple‐Decker Complexes

Abstract

As ystematic studyo nt he reactivity of the triple-decker complex [(Cp'''Co) 2 (m,h 4

Redox Chemistry of Heterobimetallic Polypnictogen Triple‐Decker Complexes – Rearrangement, Fragmentation and Transfer

“…The heterobimetallic triple-decker complexes [(Cp*Fe)(Cp'''Co)(μ,η 5 :η 4 -E 5 )] (E = P (1), As (2)) can be easily synthesized by the reaction of the cobalt toluene complex [(Cp'''Co) 2 (μ,η 4 :η 4 -C 7 H 8 )] with [Cp*Fe(η 5 -E 5 )] (E = P, As)] in gram scale. [20,21] To obtain a first overview if redox processes are accessible, cyclic voltammetry measurements were performed revealing several redox processes (cf. Supporting Information).…”

“…Both compounds can be easily prepared from the reaction of [Cp'''Ni(η 3 -E 3 )] (E = P, As) with the cobalt toluene complex [(Cp'''Co) 2 (μ,η 4 :η 4 -C 7 H 8 )] in gram scale. The synthesis of 10 was already reported [20] and the arsenic derivative 11 was prepared analogously (cf. experimental section).…”

Coordination Behavior of [Cp″2Zr(µ1:1-As4)] towards Lewis Acids

“…Another remarkable example is the pentaarsaferrocene [Cp*Fe(η 5 -As 5 )] ( VI , Scheme 1 ) [ 17 ]. After its discovery by Scherer et al in 1990, a versatile chemistry emerged [ 18 , 19 , 20 , 21 , 22 , 23 ], including, inter alia, redox- [ 19 , 20 ] and coordination chemistry [ 21 , 22 , 23 ]. Recently, our group reported the synthesis of [Cp″ 2 Zr(η 1:1 -As 4 )] ( 1 , Scheme 1 ) by the thermolysis of As 4 with [Cp″ 2 Zr(CO) 2 ] (Cp″ = 1,3-di-tertbutyl-cyclopentadienyl) [ 24 ].…”

Synthese und mehrfache Folgereaktivität von anionischen cyclo‐E3‐Ligandkomplexen (E=P, As)

“…Schema 2). [12, 14] Die Untersuchung ihrer Redoxchemie offenbart die interessante Tatsache, dass in den Monokationen [(Cp′′′Co)(Cp′′′Ni)(μ,η 3 :η 3 ‐E 3 )][FAl] (E=P, As; [FAl]=FAl{OC 6 F 10 (C 6 F 5 )} 3 ) die {Cp′′′M}‐Fragmente nicht stark am E 3 ‐Liganden gebunden sind und dass ein Umlagerungsprozess unter Bildung der homometallischen Spezies [(Cp′′′Co) 2 (μ,η 3 :η 3 ‐E 3 )][FAl] und [(Cp′′′Ni) 2 (μ,η 3 :η 3 ‐E 3 )][FAl] stattfindet [12] . Andererseits gibt die Reduktion von 3 und 4 die monoanionischen Tripeldecker‐Komplexe [K(thf) n ][(Cp′′′Co)(Cp′′′Ni)(μ,η 3 :η 3 ‐E 3 )] (E=P, As), die ihren heterobimetallischen Charakter beibehalten.…”

“…Schema 2). [12,14] Die Untersuchung ihrer Redoxchemie offenbart die interessante Tatsache,d ass in den Monokationen [(Cp'''Co)-(Cp'''Ni)(m,h 3 :h 3 -E 3 )][FAl] (E = P, As;[ FAl] = FAl{OC 6 F 10 -(C 6 F 5 )} 3 )die {Cp'''M}-Fragmente nicht stark am E 3 -Liganden gebunden sind und dass ein Umlagerungsprozess unter Bildung der homometallischen Spezies [(Cp'''Co) 2 (m,h 3…”