title: The Cobalt cyclo-P4Sandwich Complex and Its Role in the Formation of Polyphosphorus Compounds.
abstract: A synthetic approach to the sandwich complex [Cp'''Co(η4-P4)] (2) containing a cyclo-P4ligand as an end-deck was developed. Complex 2 is the missing homologue in the series of first-row cyclo-Pnsandwich complexes, and shows a unique tendency to dimerize in solution to form two isomeric P8complexes [(Cp'''Co)2(μ,η4:η2:η1-P8)] (3 and 4). Reactivity studies indicate that 2 and 3 react with further [Cp'''Co] fragments to give [(Cp'''Co)2(μ,η2:η2-P2)2] (5) and [(Cp'''Co)3P8] (6), respectively. Furthermore, complexes 2, 3, and 4 thermally decompose forming 5, 6, and the P12complex [(Cp'''Co)3P12] (7). DFT calculations on the P4activation process suggest a η3-P4Co complex as the key intermediate in the synthesis of 2 as well as in the formation of larger polyphosphorus complexes via a unique oligomerization pathway.
authors.affiliation: Institut für Anorganische Chemie, Universität Regensburg, Universitätsstrasse 31, 93040, Regensburg, Germany.
authors.forename: Fabian
authors.initials: F
authors.lastname: Dielmann
authors.affiliation: Institute of Chemistry, St. Petersburg State University, Universitetskaya nab. 7/9, 199034, St. Petersburg, Russia.
authors.forename: Alexey
authors.initials: A
authors.lastname: Timoshkin
authors.affiliation: Institut für Anorganische Chemie, Universität Regensburg, Universitätsstrasse 31, 93040, Regensburg, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Piesch
authors.affiliation: Institut für Anorganische Chemie, Universität Regensburg, Universitätsstrasse 31, 93040, Regensburg, Germany.
authors.forename: Gábor
authors.initials: G
authors.lastname: Balázs
authors.affiliation: Institut für Anorganische Chemie, Universität Regensburg, Universitätsstrasse 31, 93040, Regensburg, Germany.
authors.forename: Manfred
authors.identifier: 0000-0003-2182-5020
authors.initials: M
authors.lastname: Scheer
keywords: cobalt; coordination modes; cyclo-P4 complexes; phosphorus; sandwich complexes