Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2 (μ,η(6) :η(6) -P6 )] Towards the "Naked" Cations Cu(+) , Ag(+) , and Tl(.).
Although the cyclo-P6 complex [(Cp*Mo)2 (μ,η(6) :η(6) -P6 )] (1) was reported 30 years ago, little is known about its chemistry. Herein, we report a high-yielding synthesis of 1, the complex 2, which contains an unprecedented cyclo-P10 ligand, and the reactivity of 1 towards the "naked" cations Cu(+) , Ag(+) , and Tl(+) . Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo-P6 middle deck, the [M(1)2 ](+) complexes are described which show distorted square-planar (M=Cu(4 a), Ag(4 b)) or distorted tetrahedral coordinated (M=Cu(5)) M(+) cations. The choice of solvent enabled control over the reaction outcome for Cu(+) , as proved by powder XRD and supported by DFT calculations. The reaction with Tl(+) affords a layered two-dimensional coordination network in the solid state.
Department of Inorganic Chemistry, University of Regensburg, 93040 Regensburg (Germany).
Martin
M
Fleischmann
Department of Inorganic Chemistry, University of Regensburg, 93040 Regensburg (Germany).
Fabian
F
Dielmann
Department of Inorganic Chemistry, University of Regensburg, 93040 Regensburg (Germany).
Laurence J
LJ
Gregoriades
Nikolaev Institute of Inorganic Chemistry, Siberian Division of RAS, Acad. Lavrentyev strasse 3, 630090 Novosibirsk (Russia).|Novosibirsk State University, Pirogova strasse 2, 630090 Novosibirsk (Russia).
Eugenia V
EV
Peresypkina
Nikolaev Institute of Inorganic Chemistry, Siberian Division of RAS, Acad. Lavrentyev strasse 3, 630090 Novosibirsk (Russia).|Novosibirsk State University, Pirogova strasse 2, 630090 Novosibirsk (Russia).
Alexander V
AV
Virovets
Department of Inorganic Chemistry, University of Regensburg, 93040 Regensburg (Germany).
Sebastian
S
Huber
Institute of Chemistry, St. Petersburg State University, 198504 Old Peterhoff, St. Petersburg (Russia).
Alexey Y
AY
Timoshkin
Department of Inorganic Chemistry, University of Regensburg, 93040 Regensburg (Germany).
Gábor
G
Balázs
Department of Inorganic Chemistry, University of Regensburg, 93040 Regensburg (Germany). Manfred.scheer@ur.de.
Manfred
M
Scheer
hexaphosphabenzene; inorganic graphene; polyphosphorus complexes; solvent-controlled reactivity; weakly coordinating anions