Chiral Chelate Ligands Based on a Neopentane Framework; Introducing Indenyl and Fluorenyl Donor Groups

Vogelgesang, Joachim; Hüttner, Gottfried; Kaifer, Elisabeth; Kircher, Peter; Rutsch, Peter; Cunskis, Sven

doi:10.1002/(sici)1099-0682(199912)1999:12<2187::aid-ejic2187>3.0.co;2-b

Cited by 11 publications

(3 citation statements)

References 59 publications

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“…Since the completion of this review, some more publications of relevance to the topic have come to our attention. These include ligands − as well as complexes of titanium, ,, zirconium, ,, chromium, tungsten, molybdenum, iron, ruthenium, and rhodium. ,− …”

Section: Note Added In Proofmentioning

confidence: 99%

Cyclopentadienylmetal Complexes Bearing Pendant Phosphorus, Arsenic, and Sulfur Ligands

2000

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Section: Note Added In Proofmentioning

confidence: 99%

Cyclopentadienylmetal Complexes Bearing Pendant Phosphorus, Arsenic, and Sulfur Ligands

2000

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“…The substitution of the ligand arms in a tripodal ligand with different donor groups has recently attracted special interest since such derivatives are of particular interest for the modeling of unsymmetrically coordinated metal ions in the active centers of metalloproteines. Tripodal ligands of the type CH 3 C[(CH 2 X)(CH 2 Y)(CH 2 Z)] (X, Y, Z = PR 2 , P , NR 2 , SR, and OR) have been reported by Huttner …”

Section: Introductionmentioning

confidence: 99%

An Unsymmetrical Tripodal Ligand with NOS₂-Donor Set: Coordination Chemistry with Nickel(II) and Zinc(II)

et al. 2004

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The synthesis of the novel tripodal ligand [N(CH2CH2CH2OH)(CH2CH2SH)2] H3-4 is reported. The aliphatic tetradentate ligand is equipped with an unsymmetrical NOS2 donor set. It reacts with Ni(OAc)2 x 4H2O or Zn(BF4)2 x xH2O to give the complexes [Ni(H-4)]2 5 and [Zn(H-4)]4 6, respectively. The molecular structures of 5 and 6 have been determined by X-ray diffraction. In both cases multinuclear, mu-thiolato-bridged complexes, wherein the ligand coordinates with only three (NS2) of the four donor groups, had formed. The dinuclear complex 5 adopts a butterfly geometry and contains nickel(II) ions in a square-planar NS3 coordination environment. Cyclic voltammetry experiments indicate that the nickel centers in 5 are electron-rich but not overly sensitive toward oxidation. Complex 6 is tetranuclear and the four thiolato-bridged metal centers form a ring. It shows a distorted tetrahedral coordination geometry for the zinc(II) ions in an NS3 coordination sphere. In both complexes the hydroxyl functionalized ligand arm of the tripodal ligand remains uncoordinated.

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“…The second approach, ring slip of the cyclopentadienyl group from pentahapto to tri- or monohapto, could also allow the supporting ligand to respond to electronic changes at the metal center. Indenyl (Ind) and fluorenyl (Flu) derivatives provide coordination modes and reactivity patterns that are difficult for the parent Cp ligand system to access. − A derivative combining bis(oxazoline) and fluorenyl groups could potentially coordinate in a piano-stool configuration, bidentate C,N (Chart B, bottom), or tridentate C,N,N modes, and these coordination modes could support the multiple electronic configurations of redox-active metal centers. In addition, we thought flexibility within the anionic π donor group, via ring slip, could allow reversible coordination of pendent oxazoline groups in substitution reactions of donor ligands.…”

Section: Introductionmentioning

confidence: 99%

Redox Chemistry of Bis(oxazolinyl)cyclopentadienyl and -fluorenyl Rhodium and Iridium Organometallic Compounds

Schmidt

Basemann

et al. 2018

Organometallics

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Rhodium and iridium compounds supported by 1-cyclopentadienyl-1,1-bis(4,4-dimethyl-2-oxazolinyl)ethane (MeC(Ox Me2 ) 2 (C 5 H 4 ); Bo M Cp) form the 18-electron piano-stool compounds {Bo M Cp}ML 2 (L = C 2 H 4 , C 8 H 12 , CO) containing two noncoordinated oxazolines. Bromination of {Bo M Cp}Rh(C 2 H 4 ) 2 gives {Bo M Cp}RhBr 2 . A single-crystal X-ray diffraction study reveals that only one oxazoline is coordinated in the solid-state structure of {Bo M Cp}RhBr 2 . The oxazolines exchange rapidly on the 1 H NMR time scale at room temperature but slowly at −10 °C. In contrast, the fluorenyl derivative MeC(Ox Me2 ) 2 (C 13 H 8 ) (Bo M Flu) forms 16-electron square-planar rhodium(I) and iridium(I) complexes containing bidentate {C,N-Bo M Flu}M coordination that features a M−C single bond (i.e., monohapto-fluorenyl bonding). {Bo M Flu}Rh(η 4 -C 8 H 12 ) undergoes two electrochemically and chemically reversible one-electron redox events with E 1/2 at −640 and 220 mV. One-electron chemical oxidation provides the long-lived rhodium(II) hydrocarbyl species [{Bo M Flu}Rh(C 8 H 12 )] + , which reacts to give the monovalent species [{Bo M Flu-H}Rh(η 4 -C 8 H 12 )] + . Alternatively, one-electron oxidation of {Bo M Flu}Ir(η 4 -C 8 H 12 ) provides a transient diamagnetic iridium hydride, detected by 1 H NMR spectroscopy, that ultimately rearranges into [{Bo M Flu-H}Ir(η 4 -C 8 H 12 )] + . This process can be prevented for both congeners by employing the allylic H-free dibenzo[a,e]cyclooctatetraene (C 16 H 12 ) ligand. Oxidation of {Bo M Flu}M(η 4 -C 16 H 12 ) (M = Rh, Ir) provides [{Bo M Flu}M(η 4 -C 16 H 12 )] + with lifetimes of greater than 1 day.

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Chiral Chelate Ligands Based on a Neopentane Framework; Introducing Indenyl and Fluorenyl Donor Groups

Cited by 11 publications

References 59 publications

Cyclopentadienylmetal Complexes Bearing Pendant Phosphorus, Arsenic, and Sulfur Ligands

Cyclopentadienylmetal Complexes Bearing Pendant Phosphorus, Arsenic, and Sulfur Ligands

An Unsymmetrical Tripodal Ligand with NOS₂-Donor Set: Coordination Chemistry with Nickel(II) and Zinc(II)

Redox Chemistry of Bis(oxazolinyl)cyclopentadienyl and -fluorenyl Rhodium and Iridium Organometallic Compounds

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Chiral Chelate Ligands Based on a Neopentane Framework; Introducing Indenyl and Fluorenyl Donor Groups

Cited by 11 publications

References 59 publications

Cyclopentadienylmetal Complexes Bearing Pendant Phosphorus, Arsenic, and Sulfur Ligands

Cyclopentadienylmetal Complexes Bearing Pendant Phosphorus, Arsenic, and Sulfur Ligands

An Unsymmetrical Tripodal Ligand with NOS2-Donor Set: Coordination Chemistry with Nickel(II) and Zinc(II)

Redox Chemistry of Bis(oxazolinyl)cyclopentadienyl and -fluorenyl Rhodium and Iridium Organometallic Compounds

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An Unsymmetrical Tripodal Ligand with NOS₂-Donor Set: Coordination Chemistry with Nickel(II) and Zinc(II)