Iron phosphine catalyzed cross-coupling of tetraorganoborates and related group 13 nucleophiles with alkyl halides

Robin B. Bedford; Peter B. Brenner; Emma Carter; Jamie Clifton; Paul M. Cogswell; Nicholas J. Gower; Mairi F. Haddow; Jeremy N. Harvey; Jeffrey A. Kehl; Damien M. Murphy; Emily C. Neeve; Michael L. Neidig; Joshua Nunn; Benjamin E.R. Snyder; Joseph Taylor

doi:10.1021/om500518r

Iron phosphine catalyzed cross-coupling of tetraorganoborates and related group 13 nucleophiles with alkyl halides

Robin B. Bedford, Peter B. Brenner, Emma Carter, Jamie Clifton, Paul M. Cogswell, Nicholas J. Gower, Mairi F. Haddow, Jeremy N. Harvey, Jeffrey A. Kehl, Damien M. Murphy, Emily C. Neeve, Michael L. Neidig, Joshua Nunn, Benjamin E.R. Snyder, Joseph Taylor

Research output: Contribution to journal › Article › peer-review

Abstract

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 Mössbauer 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.

Original language	English (US)
Pages (from-to)	5767-5780
Number of pages	14
Journal	Organometallics
Volume	33
Issue number	20
DOIs	https://doi.org/10.1021/om500518r
State	Published - Oct 27 2014
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om500518r

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Bedford, R. B., Brenner, P. B., Carter, E., Clifton, J., Cogswell, P. M., Gower, N. J., Haddow, M. F., Harvey, J. N., Kehl, J. A., Murphy, D. M., Neeve, E. C., Neidig, M. L., Nunn, J., Snyder, B. E. R., & Taylor, J. (2014). Iron phosphine catalyzed cross-coupling of tetraorganoborates and related group 13 nucleophiles with alkyl halides. Organometallics, 33(20), 5767-5780. https://doi.org/10.1021/om500518r

Bedford, RB, Brenner, PB, Carter, E, Clifton, J, Cogswell, PM, Gower, NJ, Haddow, MF, Harvey, JN, Kehl, JA, Murphy, DM, Neeve, EC, Neidig, ML, Nunn, J, Snyder, BER & Taylor, J 2014, 'Iron phosphine catalyzed cross-coupling of tetraorganoborates and related group 13 nucleophiles with alkyl halides', Organometallics, vol. 33, no. 20, pp. 5767-5780. https://doi.org/10.1021/om500518r

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title = "Iron phosphine catalyzed cross-coupling of tetraorganoborates and related group 13 nucleophiles with alkyl halides",

abstract = "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 M{\"o}ssbauer 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.",

author = "Bedford, {Robin B.} and Brenner, {Peter B.} and Emma Carter and Jamie Clifton and Cogswell, {Paul M.} and Gower, {Nicholas J.} and Haddow, {Mairi F.} and Harvey, {Jeremy N.} and Kehl, {Jeffrey A.} and Murphy, {Damien M.} and Neeve, {Emily C.} and Neidig, {Michael L.} and Joshua Nunn and Snyder, {Benjamin E.R.} and Joseph Taylor",

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AU - Bedford, Robin B.

AU - Brenner, Peter B.

AU - Carter, Emma

AU - Clifton, Jamie

AU - Cogswell, Paul M.

AU - Gower, Nicholas J.

AU - Haddow, Mairi F.

AU - Harvey, Jeremy N.

AU - Kehl, Jeffrey A.

AU - Murphy, Damien M.

AU - Neeve, Emily C.

AU - Neidig, Michael L.

AU - Nunn, Joshua

AU - Snyder, Benjamin E.R.

AU - Taylor, Joseph

PY - 2014/10/27

Y1 - 2014/10/27

N2 - 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 Mössbauer 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.

AB - 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 Mössbauer 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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Iron phosphine catalyzed cross-coupling of tetraorganoborates and related group 13 nucleophiles with alkyl halides

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