Metal‐Assisted Opening of Intact P4 Tetrahedra

Modl M, Heinl S, Balázs G, Delgado Calvo F, Caporali M, Manca G, Keilwerth M, Meyer K, Peruzzini M, Scheer M (2019)

Publication Type: Journal article

Publication year: 2019

Journal

Chemistry - A European Journal Wiley

DOI: 10.1002/chem.201900778

Abstract

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.

Authors with CRIS profile

Martin Keilwerth Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Universität Regensburg DE Germany (DE) Consiglio Nazionale delle Ricerche (CNR) / National Research Council of Italy IT Italy (IT)

How to cite

APA:

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. https://dx.doi.org/10.1002/chem.201900778

MLA:

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

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