Etude par spectroscopie raman de resonance du schema de coordination du fer de derives ferriporphyriniques a liaison σ metal-carbone

Tabard, Alain; Lagrange, G.; Guilard, Roger; Jouan, M.; Dao, Nguyen Quy

doi:10.1016/s0022-328x(00)99732-8

Cited by 7 publications

(5 citation statements)

References 27 publications

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“…The high-spin situation involves occupation of M−L σ*-orbitals. No solvent coordination to these system has been observed; however, the spin state is found to be solvent dependent at low temperature …”

Section: Viii4 D5 Systemsviii41 15-electron Systemsmentioning

confidence: 91%

“…perfluorinated) organic ligand and/or basic porphyrins, 130,131 and cases of a spin equilibrium have also been reported. 598 The high-spin situation involves occupation of M-L σ*-orbitals. No solvent coordination to these system has been observed; however, the spin state is found to be solvent dependent at low temperature.…”

Section: Viii41 15-electron Systemsmentioning

confidence: 99%

“…No solvent coordination to these system has been observed; however, the spin state is found to be solvent dependent at low temperature. 598 Porphyrin derivatives of Ru(III), e.g. Ru(TPP)Ph and Ru(OEP)Ph, CXXXIX, assumed to have a S ) 1 / 2 ground state are also known.…”

Section: Viii41 15-electron Systemsmentioning

confidence: 99%

“…Five-coordinate (σ-organo)iron(III) are well represented in the extensively investigated class of alkyl and arylporphyrinato complexes, which adopt a square-pyramidal structure with the organic ligand occupying the apical position, CXXXIX . − ,− These compounds are generally low-spin (S = 1 / 2 ), but can also adopt a high spin (S = 5 / 2 ) ground state in conjunction with electron-withdrawing (e.g. perfluorinated) organic ligand and/or basic porphyrins, , and cases of a spin equilibrium have also been reported . The high-spin situation involves occupation of M−L σ*-orbitals.…”

Section: Viii4 D5 Systemsviii41 15-electron Systemsmentioning

confidence: 99%

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Open-Shell Organometallics as a Bridge between Werner-Type and Low-Valent Organometallic Complexes. The Effect of the Spin State on the Stability, Reactivity, and Structure

1996

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Section: Viii4 D5 Systemsviii41 15-electron Systemsmentioning

confidence: 91%

Section: Viii41 15-electron Systemsmentioning

confidence: 99%

Section: Viii41 15-electron Systemsmentioning

confidence: 99%

Section: Viii4 D5 Systemsviii41 15-electron Systemsmentioning

confidence: 99%

See 2 more Smart Citations

Open-Shell Organometallics as a Bridge between Werner-Type and Low-Valent Organometallic Complexes. The Effect of the Spin State on the Stability, Reactivity, and Structure

1996

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“…The sharp features in the 3300-3400 G range (g 2) are typical of low-spin Fe III (S 5 1 =2), similar features being reported for low spin alkyl iron(III) porphyrin derivatives. [57][58][59] The presence of Fe(acac) 3 in the sample can be easily explained as resulting from homolytic cleavage of the thermally labile PVAc-Fe III (acac) 2 bond, yielding Fe(acac) 2 , which is known to transform to Fe(acac) 3 in moist air, 46 as already mentioned above. Thus, the EPR study confirms the presence of thermally labile slow-spin Fe III centers, and it indirectly points to the presence of the Fe III (acac) 2 unit r bonded to the PVAc chain at the x end, although this cannot be considered as definite and unambiguous proof.…”

Section: Articlementioning

confidence: 89%

Organometallic mediated radical polymerization of vinyl acetate with Fe(acac)₂

Xue

Poli

2013

J. Polym. Sci. Part A: Polym. Chem.

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The radical polymerization of vinyl acetate (VAc) is moderated by iron(II) acetylacetonate (Fe(acac) 2 ) by the organometallic route (OMRP), as well as by degenerative transfer polymerization (DTP) 1,2 a representative example of controlled radical polymerization, has become a tool in controlling the polymerization of less reactive monomers such as vinyl acetate (VAc). OMRP rests on the use of organometallic dormant species that can easily and reversibly generate the growing radical chain by homolytic cleavage of the metal-carbon bond. This may be possible either by direct dissociative bond breaking, as shown in Scheme 1, or by associative radical exchange (also known as degenerative transfer) if an independent radical source is available and if the metal coordination sphere allows it, Scheme 2. Hence, organometallic chemistry is of great relevance in controlled radical polymerization, but rather than strong metal-carbon bonds that impart thermal stability and robustness to the molecule and allows its manipulation and use under a broad range of experimental conditions, weak metal-carbon bonds leading to thermally fragile systems are necessary here.

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Synthesis, electrochemistry, and structural properties of porphyrins with metal-carbon single bonds and metal-metal bonds

Guilard

Lecomte

Kadish

1987

Structure and Bonding

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Porphyrins are known to coordinate with most of the metallic or pseudo-metaUic elements. However, in spite of the large number of isolated metaUoporphyrin derivatives, metal-carbon o-bonded complexes are limited only to the following series: Fe, Ru, Co, Rh, Ir, Ti, A1, Ga, In, T1, Si, Ge, Sn, and Zn.These complexes are of great interest as model compounds for understanding the functions and relationships of several biological macromolecules, as well as for their chemical reactivity. In the latter case the insertion of small molecules between the metal ion and the carbon atom may result in activation of the inserted molecule or may generate new monomeric or polymeric materials. In addition, metal-carbon o-bonded porphyrins can act as precursors in the synthesis of metal-metal bonded derivatives.This review will cover the general strategies for synthesizing organometallic porphyrin complexes. Furthermore, we will also discuss the electrochemical and structural properties of metalloporphyrins from the viewpoint of organometallic chemistry. In doing this we will focus on the following points: (i) We will give a summary of the synthetic procedures and characteristics of metal-alkyi (aryl) o-bonded porphyrins. Special emphasis will be placed on the magnetic properties of the ironcarbon porphyrin derivatives. (ii) The insertion of carbon dioxide and sulfur dioxide into the metal-carbon bond of metalloporphyrins containing main group metals such as Ga, In, and Al will be discussed. (iii) The synthesis of metal-metal bonded metalloporphyrins containing a o-bond or a donor-acceptot bond will be presented; we will also focus on the structural and electrochemical properties of some typical compounds.

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Etude par spectroscopie raman de resonance du schema de coordination du fer de derives ferriporphyriniques a liaison σ metal-carbone

Cited by 7 publications

References 27 publications

Open-Shell Organometallics as a Bridge between Werner-Type and Low-Valent Organometallic Complexes. The Effect of the Spin State on the Stability, Reactivity, and Structure

Open-Shell Organometallics as a Bridge between Werner-Type and Low-Valent Organometallic Complexes. The Effect of the Spin State on the Stability, Reactivity, and Structure

Organometallic mediated radical polymerization of vinyl acetate with Fe(acac)₂

Synthesis, electrochemistry, and structural properties of porphyrins with metal-carbon single bonds and metal-metal bonds

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Etude par spectroscopie raman de resonance du schema de coordination du fer de derives ferriporphyriniques a liaison σ metal-carbone

Cited by 7 publications

References 27 publications

Open-Shell Organometallics as a Bridge between Werner-Type and Low-Valent Organometallic Complexes. The Effect of the Spin State on the Stability, Reactivity, and Structure

Open-Shell Organometallics as a Bridge between Werner-Type and Low-Valent Organometallic Complexes. The Effect of the Spin State on the Stability, Reactivity, and Structure

Organometallic mediated radical polymerization of vinyl acetate with Fe(acac)2

Synthesis, electrochemistry, and structural properties of porphyrins with metal-carbon single bonds and metal-metal bonds

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Organometallic mediated radical polymerization of vinyl acetate with Fe(acac)₂