(Di‐<i>tert</i>‐butylphosphanylethyl)cyclopentadienylnickel Chelates with Alkyl, Alkenyl, Aryl, and Alkynyl Ligands: Hints to Cumulenylidene Resonance Forms

Kohser, Stefanie; Butenschön, Holger

doi:10.1002/ejic.201701172

Cited by 6 publications

(4 citation statements)

References 84 publications

(107 reference statements)

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“…[17,18] We have investigated complexes such as 2-5 with cobalt, nickel and iron as the metal centers for a long time (Scheme 2). [4,5,17,[19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] Here we report some new reactions of cyclopentadienylnickel complexes with a secondary phosphane tether.…”

Section: Introductionmentioning

confidence: 99%

New Reactions of Cyclopentadienylnickel Chelates with Secondary Phosphane Tethers

2021

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In continuation of our research in cyclopentadienylalkylphosphane nickel chelates with secondary phosphane tethers the first cationic representatives of this class of compounds are reported. These were obtained by reaction of the respective bromo complex with tris(4-trifluoromethylphenyl)phosphane as well as with a number of alkyl and aryl isonitriles in the presence of indium tribromide. This Lewis acid is crucial for the success of the reactions leading to the respective tetrabromoindate salts. The compounds were characterized spectroscopically, including rare 14 N, 13 C couplings being observed. Finally, deprotonation experiments are reported, which provide some evidence for deprotonation taking place, although the expected phosphinidene chelates could not be isolated due to rapid decomposition.

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Section: Introductionmentioning

confidence: 99%

New Reactions of Cyclopentadienylnickel Chelates with Secondary Phosphane Tethers

2021

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“…The synthesis of organometallic ring molecules has been explored for possible new functions derived from the metal elements. − Nonlinear metal coordination geometries are an advantage for the cyclization. Cyclopentadienyl (Cp) metal carbonyl complexes bearing a pendant phosphorus have a piano-stool coordination geometry and can undergo an intramolecular phosphorus–metal coordination producing ring molecules. , In addition to the small rings, cyclic macromolecular structures have also been made via metal coordination, but the resultant metal-coordinated structures are usually rigid without viscoelastic properties characteristic of polymer materials.…”

Section: Introductionmentioning

confidence: 99%

Competition between Ring-Closing Migratory Insertion Polymerization and Monomer Cyclization

et al. 2020

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Migratory insertion polymerization (MIP) of P FpR [ P Fp = (PPh 2 (CH 2 ) 3 Cp)Fe(CO) 2 , R = (CH 2 ) 4 CHCH 2 or (CH 2 ) 5 CH 3 ] (1) involved competitive MIP ring-closing polymerization and monomer cyclization (MC), producing P( P FpR) macrocycles (2) and P FpR rings (3), respectively. MC, generating 3, occurred at the early stage of MIP, while the growing polymer chains exclusively underwent ring-closing cyclization without producing any linear analogues. The effect of solvent, temperature, and the concentration of 1 on the competition between the ringclosing MIP and MC was investigated. 3 was synthesized as the only product in THF with a low concentration of 1 (1 wt %), while the ring-closing MIP predominated under the condition at 60 °C with a high concentration of 1 in THF (>70 wt %), resulting in 2 with M n up to 17 500 g/mol. This effective synthesis of ring molecules is attributed to the piano-stool coordination geometry and the low rotation barrier of Cp−Fe bond and will facilitate further exploration of ring molecules as functional materials and supramolecular building blocks.

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“…[9] Nickel chelate 2 was obtained by treatment of the anionic ligand system with nickel(II) chloride and allowed the formation of a number of derivatives by replacement of the chloro ligand. [10,11] 3 is the first η 5 -indenylnickel chelate complex with a pendant phosphane tether. [12] Compound 4 is an example of a complex with non-coordinated phosphane tethers, [13] which is an interesting diphosphane ligand.…”

Section: Introductionmentioning

confidence: 99%

“…Cobalt chelate 1 was the starting material for a number of reactions, e. g. leading to vinylidene complexes,, metallacycles, fission of a C,P triple bond,, and the catalytic [2+2+2] cyclotrimerization of alkynes in aqueous solvent . Nickel chelate 2 was obtained by treatment of the anionic ligand system with nickel(II) chloride and allowed the formation of a number of derivatives by replacement of the chloro ligand , . 3 is the first η 5 ‐indenylnickel chelate complex with a pendant phosphane tether .…”

Section: Introductionmentioning

confidence: 99%

1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane: Synthesis, Reactions and Mössbauer Spectroscopy

et al. 2018

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1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane was prepared in 76% yield by deprotonation of 1,1’‐di(2‐tert‐butylphosphanylethyl)ferrocene followed by treatment with 1,1’‐di(2‐bromoethyl)ferrocene. The ferrocenophane exists as a mixture of syn and anti diastereomers, which were separated by repeated precipitation of one of them. Reaction with borane afforded the respective borane adducts in 47% yield. Methylation with iodomethane gave the respective diphosphonium salt in quantitative yield. Oxidation with 1.0 or 5.0 equivalents of silver hexafloroantimonate gave a green and a blue material, respectively, presumably the mono and the diferrcenium salts. 1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane and its oxidation products were subjected to a temperature‐dependent Mössbauer effect (ME) study to elucidate their dynamical and paramagnetic relaxation characteristics. The ME data are consistent with the absence of spin averaging for the two distinct Fe sites in the monooxidation product over the temperature range 91

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(Di‐tert‐butylphosphanylethyl)cyclopentadienylnickel Chelates with Alkyl, Alkenyl, Aryl, and Alkynyl Ligands: Hints to Cumulenylidene Resonance Forms

Cited by 6 publications

References 84 publications

New Reactions of Cyclopentadienylnickel Chelates with Secondary Phosphane Tethers

New Reactions of Cyclopentadienylnickel Chelates with Secondary Phosphane Tethers

Competition between Ring-Closing Migratory Insertion Polymerization and Monomer Cyclization

1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane: Synthesis, Reactions and Mössbauer Spectroscopy

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