Synthesis, Structure, and Reactivity of Organo-Iron(II) Complexes with N-Heterocyclic Carbene Ligation

Li, Xiang; Xiao, Jie; Deng, Liang

doi:10.1021/om2000663

Cited by 99 publications

(120 citation statements)

References 81 publications

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“…The underligated complexes 20, 23, 26, 31 and 32 have been previously reported by us [66][67][68]; all other complexes shown in Scheme 12 are new. The complex [Fe(NHC) Mes 2 ], where NHC = N,N'-diisopropyl-imidazol-2-ylidene, was reported simultaneously with our work [69]. The thermally stable 12 valence electron dialkyl complexes undergo IPr or (S)IPr substitution by (S)IMes to give the analogous 3-coordinate complexes (one example, 29, is shown in Scheme 12).…”

Section: N1 Fe1 Cl1supporting

confidence: 59%

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

Danopoulos

Braunstein

2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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Dedicated to the memory of Yves Chauvin, a most remarkable and visionary man and scientist, with gratitude for our scientific and non-scientific conversations and a very fruitful and enjoyable collaboration.Abstract -Two major aspects of coordination/organometallic chemistry are discussed in this article: (i) the use of functional chelating ligands to stabilize metal complexes while allowing easy stereodifferentiation within the coordination sphere and (ii) the choice of suitable ligands to stabilize challenging 'underligated' metal complexes with electronically highly unsaturated metal centres, thus potentially displaying unusual reactivity. In both cases, the relevance to homogeneous catalysis will be discussed.Résumé -Contrôle de la sphère de coordination des métaux par les ligands : structures, réacti-vité et catalyse -Deux aspects majeurs de la chimie de coordination/organométallique sont discutés dans cet article : d'une part, l'utilisation de ligands chélatants fonctionnels pour stabiliser des complexes métalliques en permettant une différenciation stéréoélectronique aisée au sein de la sphère de coordination et, d'autre part, la sélection de ligands adaptés à la stabilisation de complexes métalliques sous-coordinés dont les centres métalliques sont hautement insaturés électroniquement et donc potentiellement le siège d'une réactivité inhabituelle. Dans les deux cas, nous évoquerons la pertinence de ces approches en catalyse homogène.

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Section: N1 Fe1 Cl1supporting

confidence: 59%

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

Danopoulos

Braunstein

2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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“…The Fe−C(carbene) separations in 3t−6t also span the narrow range from 2.137(2) to 2.162(2) Å and are close to those of the reported four-coordinate high-spin iron(II) NHC complexes. 17,19 Besides the similar bond distances, the range of the C−Fe−C angles and the relative orientation of the aryl and imidazole planes in 3t−6t are different. These distinctions might be caused by crystal-packing force and the different steric properties of the aryl ligands.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Four-Coordinate Iron(II) Diaryl Compounds with Monodentate N-Heterocyclic Carbene Ligation: Synthesis, Characterization, and Their Tetrahedral-Square Planar Isomerization in Solution

et al. 2015

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The salt elimination reactions of (IPr2Me2)2FeCl2 (IPr2Me2 = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) with the corresponding aryl Grignard reagents afford [(IPr2Me2)2FeAr2] (Ar = Ph, 3; C6H4-p-Me, 4; C6H4-p-(t)Bu, 5; C6H3-3,5-(CF3)2, 6) in good yields. X-ray crystallographic studies revealed the presence of both tetrahedral and trans square planar isomers for 3 and 6 and the tetrahedral structures for 4 and 5. Magnetic susceptibility and (57)Fe Mössbauer spectrum measurements on the solid samples indicated the high-spin (S = 2) and intermediate-spin (S = 1) nature of the tetrahedral and square planar structures, respectively. Solution property studies, including solution magnetic susceptibility measurement, variable-temperature (1)H and (19)F NMR, and absorption spectroscopy, on 3-6, as well as an (57)Fe Mössbauer spectrum study on a frozen tetrahydrofuran solution of tetrahedral [(IPr2Me2)2(57)FePh2] suggest the coexistence of tetrahedral and trans square planar structures in solution phase. Density functional theory calculations on (IPr2Me2)2FePh2 disclosed that the tetrahedral and trans square planar isomers are close in energy and that the geometry isomerization can occur by spin-change-coupled geometric transformation on four-coordinate iron(II) center.

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“…15 Only one example of a three-coordinate iron carbene has been previously reported. 16 To obtain deeper insight into the structure and bonding in 2 and 3, a computational analysis was carried out. Our aim was to quantify the strengths of the Fe-C bonds, and to determine the orbital interactions that contribute towards (de)stabilization of these bonds.…”

Section: Dmentioning

confidence: 99%

Structure and bonding in three-coordinate N-heterocyclic carbene adducts of iron(ii) bis(trimethylsilyl)amide

et al. 2011

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The molecular structures, chemical bonding and magnetochemistry of the three-coordinate iron(II) NHC complexes [(NHC)Fe{N(SiMe 3 ) 2 } 2 ] (NHC = IPr, 2; NHC = IMes, 3) are reported.N-Heterocyclic carbene (NHC) complexes of late transition metals such as ruthenium, palladium and gold are an intensely studied class of compound owing to their applications in catalysis. [1][2][3] In contrast, studies of iron NHC complexes are less widespread. A series of recent reports has, however, shown that NHC complexes of iron do have considerable potential for development in a range of carbon-carbon and carbonheteroatom bond forming reactions. 4 In most cases, the nature of the active iron NHC complex is not known, but it is probable that low-coordinate iron NHC complexes play an important role.

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Synthesis, Structure, and Reactivity of Organo-Iron(II) Complexes with N-Heterocyclic Carbene Ligation

Cited by 99 publications

References 81 publications

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

Four-Coordinate Iron(II) Diaryl Compounds with Monodentate N-Heterocyclic Carbene Ligation: Synthesis, Characterization, and Their Tetrahedral-Square Planar Isomerization in Solution

Structure and bonding in three-coordinate N-heterocyclic carbene adducts of iron(ii) bis(trimethylsilyl)amide

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