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.

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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://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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