Bis(η5-hydropentalenyl)iron

Molins, Elı́es; Maniukiewicz, Waldemar; Miravitlles, C.; Mas, M.; Manríquez, J.; Chávez, Ivonne; Oelckers, Beatriz; Farran, Joan; Briansó, J. L.

doi:10.1107/s0108270196005872

Cited by 5 publications

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“…These sandwich structures have very similar geometries around the Fe centre, with metalcentroid distances and near linear centroidmetalcentroid angles which are consistent with ferrocene and its pentalene analogues that have been previously determined by X-ray diffraction studies. [20][21][22][23][24] Removal of an allylic proton from 1 to form 2 results in a formal negative charge on the five membered ring of the coordinated pentalene ligand, to which potassium coordinates in an This is consistent with a localised double bond, and similar values are found in previously reported hydropentalenyl compounds [27] (dC=C = 1.329(8), 1.377(9) and 1.354(7) Å respectively).…”

Section: Iron Bis(pentalene) Complexessupporting

confidence: 80%

Complexes of iron(II) with silylated pentalene ligands; building blocks for homo- and heterobimetallics

et al. 2016

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(2016) Complexes of Iron(II) with silylated pentalene ligands; building blocks for homo-and heterobimetallics. Polyhedron, This version is available from Sussex Research Online: http://sro.sussex.ac.uk/59846/ This document is made available in accordance with publisher policies and may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the URL above for details on accessing the published version. Copyright and reuse:Sussex Research Online is a digital repository of the research output of the University.Copyright and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable, the material made available in SRO has been checked for eligibility before being made available.Copies of full text items generally can be reproduced, displayed or performed and given to third parties in any format or medium for personal research or study, educational, or not-for-profit purposes without prior permission or charge, provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. DFT calculations on model mono-Fe(η 5 -Pn) compounds reveal the charge densities on the uncoordinated carbon atoms of the pentalene ligand, and hence the potential for incorporating these units into heteronuclear bimetallic complexes is assessed.

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Section: Iron Bis(pentalene) Complexessupporting

confidence: 80%

Complexes of iron(II) with silylated pentalene ligands; building blocks for homo- and heterobimetallics

et al. 2016

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“…Additionally, the C32-C33 distance is found to be noticeably shorter at 1.354 (7) Å than the other C-C distances in the pentalene skeleton (av 1.449(7) Å), which is consistent with a localized double bond and is similar to that found in the Mn(II) complex [Mn 2 (C 8 H 4 {Si i Pr 3 -1,4} 2 ) 2 ] (1.383(7) Å) 6 and hydropentalenyl compounds [Fe(η 5 :η 5 -C 8 H 7 ) 2 ] and [Re(CO) 3 (η 5 -C 8 H 7 )] (CdC 1.329(8)-1.377(9) Å). [7][8][9] Although hydropentalenyl compounds are known to be formed from hydropentalenyl starting materials, it is rare that one is derived from the pentalenyl dianion.…”

Section: Resultsmentioning

confidence: 99%

Samarium(III) Pentalene Sandwich Compounds [Sm(η⁸-C₈H₄{SiⁱPr₃-1,4}₂)(Cp*)] and [Sm(η⁸-C₈H₄{SiⁱPr₃-1,4}₂)(η⁵-C₈H₅{SiⁱPr₃-1,4}₂)] and a Mixed-Valence Hexasamarium Cluster Derived from Sm(II)-Based Solvent Activation

et al. 2008

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The reaction of the pentalene salt C8H4{SiiPr3-1,4}2[K]2 with [SmCp*(μ-I)(THF)2]2 yields not the expected Sm(II) pentalene-bridged dimer but the Sm(III) sandwich complexes [Sm(η8-C8H4{SiiPr3-1,4}2)(η5-Cp*)] (1) and [Sm(η8-C8H4{SiiPr3-1,4}2)(η5-C8H5{SiiPr3-1,4}2)] (2) and the mixed-valence cluster [Cp*6Sm6(OMe)8O][K(THF)6] (3) via solvent activation of THF. The samarium(III) sandwich compound 2 incorporates an η8-pentalene ligand and an η5-hydropentalenyl ligand. X-ray crystallography shows the Sm(II)/Sm(III) mixed-valence cluster compound 3 to contain a centrosymmetric hexanuclear array of Cp*Sm units, bridged by face-centered μ3-methoxy groups, with a central oxo unit.

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“…X-ray-quality single crystals were grown from Et 2 O solution; the structure of 6 is shown in Figure , and important bond lengths are given in Table . The ligand is not planar, with a hinge angle of 5.6° (defined as the angle between the least-squares planes containing atoms C1, C2, C3, C7, C8 and C4, C5, C6, C7, C8, respectively) directing the uncoordinated ring away from the metal center.…”

Section: Resultsmentioning

confidence: 99%

Convenient Solution Route To Alkylated Pentalene Ligands: New Metal Monoalkylpentalenyl Complexes

et al. 2005

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Carbene-induced rearrangement of 8,8-dibromobicyclo[5.1.0]octa-2,4-dienes and subsequent in situ deprotonation of the dihydropentalenes formed represents a straightforward and versatile solution route to pentalene ligands for use in organometallic chemistry. We report here the synthesis of 6-alkyl-substituted 8,8-dibromobicyclo[5.1.0]octa-2,4-dienes and their rearrangement to give correspondingly substituted pentalene ligands. Generation of methyl-substituted dihydropentalenes from 8,8-dibromo-6-methylbicyclo-[5.1.0]octa-2,4-diene followed by monodeprotonation with TlOEt gives methylhydropentalenyl salts, Tl-(C 8 H 6 Me), as a mixture of isomers. Formation of both 1-Me and 3-Me isomers of Re(C 8 H 6 Me)(CO) 3 from these Tl species shows that monodeprotonation of the dihydropentalenes occurs at the unsubstituted ring. No evidence for the 2-Me isomer is observed, consistent with the rearrangement mechanism reported in the literature. Likewise, rearrangement of 8,8-dibromo-6-alkylbicyclo[5.1.0]octa-2,4-dienes (R ) Me, Et, i Pr) and subsequent double deprotonation with n BuLi in the presence of DME affords the pentalenyl salts Li 2 (C 8 H 5 R)‚xDME. X-ray crystallographic studies of the dinuclear Mn organometallics anti-[Mn-(CO) 3 ] 2 (C 8 H 5 R) synthesized from the Li salts confirm that these alkylated pentalene ligands are substituted at the 1-position exclusively. The crystal structure of a model hydropentalenyl complex, Re(C 8 H 7 )(CO) 3 , is also reported.

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Bis(η5-hydropentalenyl)iron

Cited by 5 publications

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Complexes of iron(II) with silylated pentalene ligands; building blocks for homo- and heterobimetallics

Complexes of iron(II) with silylated pentalene ligands; building blocks for homo- and heterobimetallics

Samarium(III) Pentalene Sandwich Compounds [Sm(η⁸-C₈H₄{SiⁱPr₃-1,4}₂)(Cp*)] and [Sm(η⁸-C₈H₄{SiⁱPr₃-1,4}₂)(η⁵-C₈H₅{SiⁱPr₃-1,4}₂)] and a Mixed-Valence Hexasamarium Cluster Derived from Sm(II)-Based Solvent Activation

Convenient Solution Route To Alkylated Pentalene Ligands: New Metal Monoalkylpentalenyl Complexes

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Bis(η5-hydropentalenyl)iron

Cited by 5 publications

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Complexes of iron(II) with silylated pentalene ligands; building blocks for homo- and heterobimetallics

Complexes of iron(II) with silylated pentalene ligands; building blocks for homo- and heterobimetallics

Samarium(III) Pentalene Sandwich Compounds [Sm(η8-C8H4{SiiPr3-1,4}2)(Cp*)] and [Sm(η8-C8H4{SiiPr3-1,4}2)(η5-C8H5{SiiPr3-1,4}2)] and a Mixed-Valence Hexasamarium Cluster Derived from Sm(II)-Based Solvent Activation

Convenient Solution Route To Alkylated Pentalene Ligands: New Metal Monoalkylpentalenyl Complexes

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Samarium(III) Pentalene Sandwich Compounds [Sm(η⁸-C₈H₄{SiⁱPr₃-1,4}₂)(Cp*)] and [Sm(η⁸-C₈H₄{SiⁱPr₃-1,4}₂)(η⁵-C₈H₅{SiⁱPr₃-1,4}₂)] and a Mixed-Valence Hexasamarium Cluster Derived from Sm(II)-Based Solvent Activation