Tetrakis(ethylene)irondilithium and Bis(η<sup>4</sup>‐1,5‐cy‐clooctadiene)irondilithium

Jonas, Klaus; Schieferstein, Ludwig; Krüger, Carl; Tsay, Yi‐Hung

doi:10.1002/anie.197905501

Cited by 77 publications

(36 citation statements)

References 8 publications

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“…It has a covalent-bond character between the Fe and Mg centers. Such an observation supported the idea that iron can remain covalently bonded to magnesium in [Fe(MgX) 2 ], the "Inorganic Grignard Reagent" (173,198). They found that finely dispersed Fe(0)* particles in THF dissolved slowly on treatment with an excess of nC 14 H 29 MgBr and the resulting solution catalyzed the crosscoupling reaction (Scheme 131).…”

Section: J Mechanism Of Cross-coupling Reactionssupporting

confidence: 64%

“…This reaction tolerated various functional groups (e.g., esters, ketone, nitriles, isocyanides, or tert-amines) ( Table XXI). A low-valent iron-catalyst can be synthesized on a large scale as an air-sensitive crystalline material on treatment of ferrocene with lithium under an ethene atmosphere (173). Following the initial report from Fürstner and coworkers (172), a variety of catalyst systems were synthesized by only varying the ligand sets.…”

Section: Low-valent Iron Complex In Cross-coupling Reactionsmentioning

confidence: 99%

“…Fürstner et al (199) proposed the formation of a low-valent ferrate complex as the active species for their cross-coupling reactions based on their experimental data and literature reports (173,198). At first, there was an in situ formation of [Fe ( II) (MgX) 2 ] (ferrate complex) and subsequently it was oxidatively added between the R-X bond.…”

Section: J Mechanism Of Cross-coupling Reactionsmentioning

confidence: 99%

“…It was observed that nucleophiles (e.g., MeLi, PhLi, or PhMgBr) were unable to undergo β-hydride elimination. Rather, they rapidly reduce Fe 3+ to Fe 2+ and then alkylated (173). However, the nucleophile, which underwent β-hydride elimination, was likely to follow a lowvalent ferrate mechanism.…”

Section: J Mechanism Of Cross-coupling Reactionsmentioning

confidence: 99%

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Iron Catalysis in Synthetic Chemistry

Rana

Modak

Maity

et al. 2014

Progress in Inorganic Chemistry: Volume 59

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Section: J Mechanism Of Cross-coupling Reactionssupporting

confidence: 64%

Section: Low-valent Iron Complex In Cross-coupling Reactionsmentioning

confidence: 99%

Section: J Mechanism Of Cross-coupling Reactionsmentioning

confidence: 99%

Section: J Mechanism Of Cross-coupling Reactionsmentioning

confidence: 99%

See 2 more Smart Citations

Iron Catalysis in Synthetic Chemistry

Rana

Modak

Maity

et al. 2014

Progress in Inorganic Chemistry: Volume 59

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“…For the known complexes that contain iron in a formally negative oxidation state with solely olefinic ligands, see: Jonas ( , 1981; Jonas et al (1979); Jonas & Krü ger (1980); Brennessel et al (2007). For the various syntheses of the cobalt analog of the title complex, see: Brennessel et al (2006); Brennessel & Ellis (2012).…”

Section: Related Literaturementioning

confidence: 99%

(18-Crown-6)potassium [(1,2,5,6-η)-cycloocta-1,5-diene][(1,2,3,4-η)-naphthalene]ferrate(−I)

Brennessel¹,

Ellis²

2012

Acta Cryst E

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The title salt, [K(C12H24O6)][Fe(C8H12)(C10H8)], is the only known naphthalene complex containing iron in a formally negative oxidation state. Each (naphthalene)(1,5-cod)ferrate(−I) anion is in contact with one (18-crown-6)potassium cation via K⋯C contacts to the outer four carbon atoms of the naphthalene ligand (cod = 1,5-cyclooctadiene, 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane). When using the midpoints of the coordinating olefin bonds, the overall geometry of the coordination sphere around iron can be best described as distorted tetrahedral. The naphthalene fold angle between the plane of the iron-coordinating butadiene unit and the plane containing the exo-benzene moiety is 19.2 (1)°.

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Dianionic Iron and Ruthenium(2−) Biphosphinine Complexes: A Formal d10 Ruthenium Complex with a Square Planar Geometry

et al. 2001

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Though the Collmans reagent [Fe(CO) 4 ] 2À is probably one of the most popular and useful reagents in organic synthesis, [1] our knowledge of dianionic Group 8 metal complexes still remains limited. In addition to the carbonyl ruthenium analogue [Ru(CO) 4 ] 2À , only a few other complexes are known: the complete series of PF 3 derivatives [M(PF 3 ) 4 ] 2À (M Fe, Ru, Os), [2] the isocyanide complexes [Ru(CNR) 4 ] 2À synthesized by Cooper and co-workers, [3] and the amazing Jonas iron complexes [Fe(C 2 H 4 ) 4 ] 2À and [Fe(cod) 2 ] 2À (cod cycloocta-1,5-diene). [4] We have begun to explore the use of sophisticated phosphinine-based ligands in an effort to design phosphorus equivalents of carbonyl ligands. [5] This we recently illustrated by the successful stabilization of an Au 0 center encapsulated in a silacalix-[4]-phosphinine macrocycle [6] and the synthesis of dianionic 2,2'-biphosphinine complexes of Group 4 [7] and 9 metals. [8] Herein we report the successful stabilization of dianionic Fe and Ru 2,2'-biphosphinine complexes.All our syntheses were carried out using dianion 2 which is readily obtained by reduction of 2,2'-biphosphinine 1 (tmbp) using lithium in excess. [9] Reaction of two equivalents of 2 with one equivalent of [{FeCl 2 (thf) 1.5 } n ] or [Ru(cod)(acac) 2 ] (acac 2,4-pentanedione, acetylacetone) in THF at low temperature, yielded complexes 3 an 4, respectively, which were isolated as highly moisture and oxygen sensitive powders (Scheme 1).The formulation of these two complexes was confirmed by NMR spectroscopic data ( 1 H and 13 C). To gain more structural information, an X-ray crystal structure analysis of complex 4 was carried out (Figure 1). [10] Remarkably, the overall geometry of 4 is not tetrahedral as usually observed for ML 4 d 10 complexes, [8] but square planar; [11] the iron complex 3 is assumed to have the same structure. The two biphosphinines are roughly located in the same plane (V 7.298, V being the interplane angle) and the two cationic [Li(thf) 3 ] units are located above and below the plane in apical positions. Though the structure roughly resembles an octahedron, the Ru´´´Li separation (2.740 (3) ) is long and exceeds the sum of the covalent radii (2.60 ) indicating only a very weak, mainly P P P P Li Li THF THF THF THF THF THF P P M P P 2 a b 2-+ + 3: M = Fe 4: M = Ru 1 2 Scheme 1. Syntheses of 3 and 4: a) Li (excess), THF, 25 8C, 2 h. b) [{FeCl 2 (thf) 1.5 } n ] or [Ru(cod)(acac) 2 ], THF À 80 8C 3RT.Figure 1. Molecular structure of 4. Thermal ellipsoids are set at the 50 % probability level. The hydrogen atoms are omitted for clarity. Important distances [] and angles [8]: Ru1-P1 2.

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Tetrakis(ethylene)irondilithium and Bis(η⁴‐1,5‐cy‐clooctadiene)irondilithium

Abstract: New FeLi2‐olefin complexes, e.g. (1), have been obtained from ferrocene by directed replacement of both C5H5 ligands. (1) reacts with COD to give (COD)2FeLi2 (2) [isolated as (2)·2 DME or (2)·2TMEDA]. which completes the series (COD)2Ni…(COD)2CoLi…(COD)2FeLi2

Cited by 77 publications

References 8 publications

Iron Catalysis in Synthetic Chemistry

Iron Catalysis in Synthetic Chemistry

(18-Crown-6)potassium [(1,2,5,6-η)-cycloocta-1,5-diene][(1,2,3,4-η)-naphthalene]ferrate(−I)

Dianionic Iron and Ruthenium(2−) Biphosphinine Complexes: A Formal d10 Ruthenium Complex with a Square Planar Geometry

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Tetrakis(ethylene)irondilithium and Bis(η4‐1,5‐cy‐clooctadiene)irondilithium

Abstract: New FeLi2‐olefin complexes, e.g. (1), have been obtained from ferrocene by directed replacement of both C5H5 ligands. (1) reacts with COD to give (COD)2FeLi2 (2) [isolated as (2)·2 DME or (2)·2TMEDA]. which completes the series (COD)2Ni…(COD)2CoLi…(COD)2FeLi2

Cited by 77 publications

References 8 publications

Iron Catalysis in Synthetic Chemistry

Iron Catalysis in Synthetic Chemistry

(18-Crown-6)potassium [(1,2,5,6-η)-cycloocta-1,5-diene][(1,2,3,4-η)-naphthalene]ferrate(−I)

Dianionic Iron and Ruthenium(2−) Biphosphinine Complexes: A Formal d10 Ruthenium Complex with a Square Planar Geometry

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Tetrakis(ethylene)irondilithium and Bis(η⁴‐1,5‐cy‐clooctadiene)irondilithium