Metal‐Assisted Opening of Intact P4 Tetrahedra

Journal article

Publication Details

Author(s): Modl M, Heinl S, Balázs G, Delgado Calvo F, Caporali M, Manca G, Keilwerth M, Meyer K, Peruzzini M, Scheer M
Journal: Chemistry - A European Journal
Publication year: 2019
ISSN: 0947-6539
eISSN: 1521-3765


The reactivity of ruthenium and manganese complexes bearing intact white phosphorus in the coordination sphere was investigated towards the low‐valent transition‐metal species [Cp′′′Co] (Cp′′′=η5‐C5H2‐1,2,4‐tBu3) and [L0M] (L0=CH[CHN(2,6‐Me2C6H3)]2; M=Fe, Co). Remarkably, and irrespective of the metal species, the reaction proceeds by the selective cleavage of two P–P edges and the formation of a square‐planar cyclo‐P4 ligand. The reaction products [{CpRu(PPh3)2}{CoCp′′′}(μ,η1:4‐P4)][CF3SO3] (5), [{CpBIGMn(CO)2}2{CoCp′′′}(μ,η1:1:4‐P4)] (6) and [{CpBIGMn(CO)2}2{ML0}(μ,η1:1:4‐P4)] (CpBIG=C5(C6H4nBu)5; L0=CH[CHN(2,6‐Me2C6H3)]2; M=Fe (7 a), Co (7 b)), respectively, were fully characterized by single‐crystal X‐ray diffraction and spectroscopic methods. The electronic structure of the cyclo‐P4 ligand in the complexes 5–7 is best described as a π‐delocalized P42− system, which is further stabilized by two and three metal moieties, respectively. DFT calculations envisaged a potential intermediate in the reaction to form 5, in which a quasi‐butterfly‐shaped P4 moiety bridges the two metals and behaves as an η3‐coordinated ligand towards the cobalt center.

FAU Authors / FAU Editors

Keilwerth, Martin
Lehrstuhl für Anorganische und Allgemeine Chemie
Meyer, Karsten Prof. Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie

External institutions
Consiglio Nazionale delle Ricerche
Universität Regensburg

How to cite

Modl, M., Heinl, S., Balázs, G., Delgado Calvo, F., Caporali, M., Manca, G.,... Scheer, M. (2019). Metal‐Assisted Opening of Intact P4 Tetrahedra. Chemistry - A European Journal.

Modl, Moritz, et al. "Metal‐Assisted Opening of Intact P4 Tetrahedra." Chemistry - A European Journal (2019).


Last updated on 2019-09-05 at 12:23