Unprecedented triphosphinine iron interactions: Intramolecular electron transfer, reactivity round a corner, and a low-activated ring element exchange reaction

Eggers K, Heinemann FW, Hennemann M, Clark T, Binger P, Zenneck U (2010)

Publication Status: Published

Publication Type: Journal article

Publication year: 2010

Journal

Publisher: Elsevier Masson

Book Volume: 13

Pages Range: 1203-1212

Journal Issue: 8-9

DOI: 10.1016/j.crci.2010.05.023

Abstract

2,4,6-Tri-tert-butyl-1,3,5-triphosphinine (7) was combined with 1,5-COD or 2,4-di-tertbutyl-1,3-diphosphete to form iron pi-complexes. The ligands of highly reactive [(2,4-di-tert-butyl-1,3-diphosphete)(2,4,6-tri-tert-butyl-1,3,5-triphosphinine)Fe] (8) are formed by cyclooligomerization of tert-butylphosphaalkyne (3) under the influence of the iron atom. 8 rearranges spontaneously to yield penta-tert-butyl-pentaphosphaferrocene (9) as the isolable product. An intramolecular electron transfer product [(1,5-COD)(eta(6)-1,3,5-triphosphacyclohexa-2,5-dine-1,4-diyl)Fe((2+))] (12) is obtained with 1,5-COD. Addition of [(CO)(5)Cr(THF)] initiates an interligand hydrogen transfer to form [(eta(5)-trihydropentalenyl)Fe(mu,1-3-eta-4,5,6-trihydro-1,3,5-triphosphinine)Cr(CO)(5)] (13) Extensive DFT calculations of isolated and reactive species, and several possible intermediates agree with the experimental observations and revealed for the first time a possible reaction sequence, which allows a low-activated exchange of ring elements between the ligands of sandwich complex 8 to form 9. The process is based on the specific combination of the metal and its heterocyclic pi-ligands. Both, singlet and triplet spin states play an important role in the process. (C) 2010 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

Authors with CRIS profile

Involved external institutions

Technische Universität Kaiserslautern Germany (DE)

How to cite

APA:

Eggers, K., Heinemann, F.W., Hennemann, M., Clark, T., Binger, P., & Zenneck, U. (2010). Unprecedented triphosphinine iron interactions: Intramolecular electron transfer, reactivity round a corner, and a low-activated ring element exchange reaction. Comptes Rendus Chimie, 13(8-9), 1203-1212. https://dx.doi.org/10.1016/j.crci.2010.05.023

MLA:

Eggers, Karin, et al. "Unprecedented triphosphinine iron interactions: Intramolecular electron transfer, reactivity round a corner, and a low-activated ring element exchange reaction." Comptes Rendus Chimie 13.8-9 (2010): 1203-1212.

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