Reduction-oxidation properties of organotransition-metal complexes. Part 8. Formation and reactivity of the radical cations [Fe(CO)3L2]+, and the mechanism of the oxidative elimination reaction of [Fe(CO)3L2] with halogens

Baker, Paul K.; Connelly, Neil G.; Jones, Brian M.; Maher, John P.; Somers, Karen R.

doi:10.1039/dt9800000579

Cited by 45 publications

(11 citation statements)

References 2 publications

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“…In the case of Fe5, the metallic centers Fe 0 are simultaneously oxidized into Fe I . This feature is in agreement with reports in the literature mentioning the reversible one-electron oxidation of P 2 Fe 0 (CO) 3 complexes in non-coordinating solvents [111]. Also in our case, full reversibility of this process was observed in CH 2 Cl 2 , while in MeCN ligand substitution probably takes places.…”

Section: The Fe Ru Os Triad With P-ligandssupporting

confidence: 94%

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

Lorcy

Bellec

Fourmigué

et al. 2009

Coordination Chemistry Reviews

255

142

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Section: The Fe Ru Os Triad With P-ligandssupporting

confidence: 94%

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

Lorcy

Bellec

Fourmigué

et al. 2009

Coordination Chemistry Reviews

255

142

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“…It has been shown that the reactions involve an initial step in which halogen radicals are formed from the alkyl halides either photochemically or thermally. These radicals react with Fe(CO) 3 L 2 in an one-electron oxidation to give the radical cation [Fe(CO) 3 L 2 ] Å+ as shown for the reaction of halogens with Fe(CO) 3 L 2 [72]. A further complication was observed for the complexes bearing ligands with terminal dimethylphosphonite groups.…”

Section: Reactions With I 2 and The Alkyl Iodides Eti N-pri And I-primentioning

confidence: 88%

Iron(0) and ruthenium(0) complexes with tridentate phosphonite ligands and their potential for ketene formation from methyl iodide, CO and a base

Jaunky

Schmalle

Blacque

et al. 2005

Journal of Organometallic Chemistry

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“…Oxidation of 1 induces a shift in ν CO of ∼40 cm –1 to 2044, 1983, 1955 cm –1 vs 2080, 2022, 1991 cm –1 . For comparison, a Δν CO value of ∼124 cm –1 is observed for the [Fe(CO) 3 (PR 3 ) 2 ] +/0 pair (R = Ph, Cy). , The observation of a single band for [Fe(CO) 3 (PR 3 ) 2 ] + has been explained in two distinct ways: retention of the D 3 h structure of its Fe(0) precursor or a distorted-square-pyramidal species that is fluxional on the IR time scale . The smaller value of Δν CO for the [ 1 ] +/0 couple is attributed to a compensating structural change that accompanies the oxidation: 1 features an η 2 -imine π acceptor, whereas [ 1 ] + features a κ 1 -imine σ donor.…”

Section: Resultsmentioning

confidence: 99%

Imine-Centered Reactions in Imino-Phosphine Complexes of Iron Carbonyls

et al. 2016

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Fundamental reactions of imino-phosphine ligands were elucidated through studies on Ph2PC6H4CHNC6H4-4-Cl (PCHNArCl) complexes of iron(0), iron(I), and iron(II). The reaction of PCHNArCl with Fe(bda)(CO)3 gives Fe(PCHNArCl)(CO)3 (1), featuring an η2-imine. DNMR studies, its optical properties, and DFT calculations suggest that 1 racemizes on the NMR time scale via an achiral N-bonded imine intermediate. The N-imine isomer is more stable in Fe(PCHNArOMe)(CO)3 (1 OMe ), which crystallized despite being the minor isomer in solution. Protonation of 1 by HBF4·Et2O gave the iminium complex [1H]BF4. The related diphosphine complex Fe(PCHNArCl)(PMe3)(CO)2 (2), which features an η2-imine, was shown to also undergo N protonation. Oxidation of 1 and 2 with FcBF4 gave the Fe(I) compounds [1]BF4 and [2]BF4. The oxidation-induced change in hapticity of the imine from η2 in [1]0 to κ1 in [1]+ was verified crystallographically. Substitution of a CO ligand in 1 with PCHNArCl gave Fe[P2(NArCl)2](CO)2 (3), which contains the tetradentate diamidodiphosphine ligand. This C–C coupling is reversed by chemical oxidation of 3 with FcOTf. The oxidized product of [Fe(PCHNArCl)2(CO)2]2+ ([4]2+) was prepared independently by the reaction of [1]+, PCHNArCl, and Fc+. The C–C scission is proposed to proceed concomitantly with the reduction of Fe(II) via an intermediate related to [2]+.

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Reduction-oxidation properties of organotransition-metal complexes. Part 8. Formation and reactivity of the radical cations [Fe(CO)3L2]+, and the mechanism of the oxidative elimination reaction of [Fe(CO)3L2] with halogens

Cited by 45 publications

References 2 publications

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

Iron(0) and ruthenium(0) complexes with tridentate phosphonite ligands and their potential for ketene formation from methyl iodide, CO and a base

Imine-Centered Reactions in Imino-Phosphine Complexes of Iron Carbonyls

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