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Issue 9, 2011
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[Cp′FeI]2 as convenient entry into iron-modified pincer complexes: bimetallic η61-POCOP-pincer iron iridium compounds

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Abstract

The synthesis of [(1,2,4-tBu3C5H2)FeI]2, [Cp′FeI]2 (1), and its reaction chemistry are described. Complex 1 shows remarkable stability toward ligand redistribution in solution and gas-phase due to kinetic stabilization with respect to Image ID:c1nj20399a-t1.gif formation. In coordinating solvents the dimer is homolytically cleaved to form paramagnetic mono-solvate 16 valence-electron (VE) adducts [Cp′FeI(L)]. These solvent adducts are labile, and 1 is re-established on exposure to dynamic vacuum. Complex 1 was demonstrated to be a suitable synthon for [Cp′Fe]+ transfer to Ir pincer complexes and successful η6-coordination of this fragment to the arene ring of κ1-metallated POCOP–iridium pincer complexes [(Cp′Fe)(POCOP)Ir(H)(I)] ([5]++) and [(Cp′Fe)(POCOP)Ir(C2H4)] ([7]++) (POCOP = C6H3-2,6-(OPtBu2)2) was accomplished. In these heterometallic organometallic complexes, the π- and σ-electrons of the POCOP-pincer phenyl anion are involved in η6- and κ1-coordination to iron(II) and iridium(III) and iridium(I), respectively. [Cp′Fe]+ coordination alters the charge distribution in the (POCOP)Ir complex by inducing significant charge transfer from the POCOP aryl π-system to the [Cp′Fe]+ fragment, and therefore yielding an electron-poor and more electrophilic iridium center. Density functional theory (DFT) calculations provide a detailed understanding of this effect. Preliminary catalytic studies show that [7]++ is an active catalyst in transfer dehydrogenation between cyclooctane (COA) and tert-butyl ethylene (TBE).

Graphical abstract: [Cp′FeI]2 as convenient entry into iron-modified pincer complexes: bimetallic η6,κ1-POCOP-pincer iron iridium compounds

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Supplementary files

Article information


Submitted
08 May 2011
Accepted
13 Jun 2011
First published
04 Jul 2011

New J. Chem., 2011,35, 1842-1854
Article type
Paper

[Cp′FeI]2 as convenient entry into iron-modified pincer complexes: bimetallic η61-POCOP-pincer iron iridium compounds

M. D. Walter and P. S. White, New J. Chem., 2011, 35, 1842
DOI: 10.1039/C1NJ20399A

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