Journal
ORGANOMETALLICS
Volume 33, Issue 20, Pages 5767-5780Publisher
AMER CHEMICAL SOC
DOI: 10.1021/om500518r
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Funding
- EPSRC
- Pfizer
- AZ-GSK-Pfizer
- Bristol Chemical Synthesis Centre for Doctoral Training
- University of Rochester
- Royal Society Wolfson Research Merit Award
- EPSRC [EP/K012258/1, EP/K013505/1, EP/K03927X/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/K013505/1, EP/K012258/1, EP/K03927X/1] Funding Source: researchfish
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Iron phosphine complexes prove to be good precatalysts for the cross-coupling of alkyl, benzyl, and allyl halides with not only aryl triorganoborate salts but also related aluminum-, gallium-, indium-, and thallium-based nucleophiles. Mechanistic studies revealed that while Fe(I) can be accessed on catalytically relevant time scales, lower average oxidation states are not formed fast enough to be relevant to catalysis. EPR spectroscopic studies reveal the presence of bis(diphosphine)iron(I) complexes in representative catalytic reactions and related processes with a range of group 13 nucleophiles. Isolated examples were studied by Mossbauer spectroscopy and single-crystal X-ray structural analysis, while the electronic structure was probed by dispersion-corrected B3LYP DFT calculations. An EPR study on an iron system with a bulky diphosphine ligand revealed the presence of an S = 1/2 species consistent with the formation of a mono(diphosphine)iron(I) species with inequivalent phosphine donor environments. DFT analysis of model complexes allowed us to rule out a T-shaped Fe(I) structure, as this is predicted to be high spin.
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