Synthesis and Coordination Chemistry of Chelate Ligands Containing Cyclopentadienyl, Indenyl and Fluorenyl Donors − Diastereoselectivity and NMR Structure Analysis

Vogelgesang, Joachim; Frick, Axel; Hüttner, Gottfried; Kircher, Peter

doi:10.1002/1099-0682(200104)2001:4<949::aid-ejic949>3.0.co;2-#

Cited by 14 publications

(3 citation statements)

References 38 publications

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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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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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“…This communication must be fast, flexible, and reliable to support multi-day, fully autonomous optimizations. The three main communication methods in Rxn Rover are LabVIEW queues, ZeroMQ universal messaging library 35 , and the implementation of the Virtual Instrument Software Architecture (VISA) standard by NI, NI-VISA 36 .…”

Section: Communicationsmentioning

confidence: 99%

“…Indenyl (Ind) and fluorenyl (Flu) derivatives provide coordination modes and reactivity patterns that are difficult for the parent Cp ligand system to access. [33][34][35][36] A derivative combining bis(oxazoline) and fluorenyl groups could potentially coordinate in a piano-stool configuration, bidentate C,N (Chart 1B, 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: Rxnmentioning

confidence: 99%

Do robots dream of electronic structures?

Basemann

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Synthesis of phosphine‐tethered indenyl ruthenium complexes through c‐h bonds activation followed by C‐C bond coupling: High performance catalysts for the redox isomerization of allylic alcohols

Deng,

Chen,

Dong

et al. 2024

Applied Organom Chemis

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Reactions of 3‐(2‐pyridyl)indene and 5‐methyl‐3‐(2‐pyridyl)indene with Ru(PPh3)3Cl2, generated two phosphine‐tethered indenyl ruthenium complexes {η5,κ1P‐(C5H4N‐C9H4R‐C6H4PPh2)}RuCl(PPh3) (R = H, 1; R = CH3, 2), respectively. While treatment of 3‐(6‐methyl‐2‐pyridyl)indene with Ru(PPh3)3Cl2 gave a product {η5‐(CH3C5H3N‐C9H6)}RuCl(PPh3)2 (3); 1 could further react with NaBArF4 to produce a cationic complex [{η5,κ1P‐(C5H4N‐C9H5‐C6H4PPh2)}Ru(PPh3)][BArF4] (15). When treated with NaOMe in methanol, 1 was converted into [{η5,κ1P‐(C5H4N‐C9H5‐C6H4PPh2)}RuH(PPh3)] (16). These five complexes were investigated as catalysts for redox isomerization of allylic alcohols, and 16 exhibited best catalytic activity in the presence of tBuOK, reaching quantitative yield in 5 min when α‐vinylbenzyl alcohol was used as the substrate, requiring catalyst loading of 1 mol%.

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Synthesis and Coordination Chemistry of Chelate Ligands Containing Cyclopentadienyl, Indenyl and Fluorenyl Donors − Diastereoselectivity and NMR Structure Analysis

Cited by 14 publications

References 38 publications

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

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

Do robots dream of electronic structures?

Synthesis of phosphine‐tethered indenyl ruthenium complexes through c‐h bonds activation followed by C‐C bond coupling: High performance catalysts for the redox isomerization of allylic alcohols

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