Transfer hydrogenation with a ferrocene diamide ruthenium complex

Elliott, Andrew G.; Green, Aaron G.; Diaconescu, Paula L.

doi:10.1039/c2dt31075a

Cited by 15 publications

(12 citation statements)

References 29 publications

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“…Currently, we are exploiting the rich chemistry enabled by flexible and redox-noninnocent ferrocene-based ligands for rare-earth metals, actinides, and other metals including late transition metals in order to study further unusual transformations and applications to material synthesis. 42,48,53,87…”

Section: ■ Summarymentioning

confidence: 99%

“…Our group has taken a different approach in order to achieve the goal of coordination flexibility and redox activity (Chart g,h). − ,− Instead of using a purely organic ligand, we reasoned that an organometallic ligand should serve as an excellent candidate. Such a ligand needs to fulfill the following requirements: (1) the organometallic part should be chemically inert under common reaction conditions; (2) the metal should be redox-active; (3) the organometallic fragment should be able to act as a weak donor.…”

Section: Introductionmentioning

confidence: 99%

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Reactivity and Properties of Metal Complexes Enabled by Flexible and Redox-Active Ligands with a Ferrocene Backbone

Huang

Diaconescu

2016

Inorg. Chem.

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Our group has focused on the organometallic chemistry of rare-earth metals and actinides for a decade. By installing ferrocene diamide ligands at electropositive metal centers, we have been able to disclose unprecedented reactivity toward aromatic N-heterocycles, arenes, and other small molecules such as P 4 . Systematic studies employing X-ray crystallography, spectroscopy, cyclic voltammetry, and DFT calculations revealed that the ferrocene backbone could stabilize the electron-deficient metal through a donor-acceptor type interaction. Most noteworthy is that this interaction can be readily turned on or off by the addition or removal of a Lewis base. In addition to its flexible coordination, the redox active nature of the ferrocene backbone enabled us to explore redox-switchable transformations. The introduction of ferrocene-based ligands into organolanthanide chemistry not only helped to study intriguing fundamental problems but also led to fruitful chemistry including small molecule activation and controlled co-polymerization reactions.3

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Section: ■ Summarymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reactivity and Properties of Metal Complexes Enabled by Flexible and Redox-Active Ligands with a Ferrocene Backbone

Huang

Diaconescu

2016

Inorg. Chem.

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“…Our group has been interested in understanding the synergistic effects resulting from the interaction of ferrocenebased ligands with metals that exist in various oxidation states. [6][7][8][9][10][11][12][13][14] We have shown that such ligands are capable of influencing bonding and enhancing reactivity of transition metals, [8][9][10][11] lanthanides, [14][15][16] as well as actinides. [17][18][19] For uranium, we have observed a wide range of reactivity between tetravalent uranium complexes supported by such ligands and heterocycles.…”

Section: Introductionmentioning

confidence: 99%

Investigation of the Electronic Structure of Mono(1,1′-Diamidoferrocene) Uranium(IV) Complexes

et al. 2013

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The electronic structure of several mono(1,1'diamidoferrocene) uranium complexes (NN R)UX2 (NN R = fc(NR)2, fc = 1,1'-ferrocenediyl, R = SiMe3, Si t BuMe2, SiMe2Ph, X = I, CH2Ph), (NN TBS)UI(OAr) (OAr = 2,6-di-tertbutylphenoxide), and (NN TBS)U(CH2Ph)(OAr) was investigated by electrochemistry, electronic absorption and vibrational spectroscopy, and DFT calculations. Similar metrical parameters were observed for (NN TBS)U(CH2Ph)2 and (NN DMP)U(CH2Ph)2 (and also for the previously reported (NN TMS)UI2(THF), (NN TBS)UI2(THF), and (NN TBS)U(CH2Ph)(OAr)) that translate in similar DFT parameters (bond orders, metal charges) despite some small differences observed by electrochemistry and IR or electronic absorption spectroscopy.

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“…The reduction of imine 10 is quantitative and the secondary amine 11 was characterized in the 1 H NMR by its H –N at 1.23 ppm and in the 15 N NMR by a signal at −332.0 ppm. Such secondary amines are valuable compounds since, notably, amido complexes are in principle accessible by simple deprotonation …”

Section: Resultsmentioning

confidence: 99%

Converging and Diverging Synthetic Strategies to Tetradentate (N,N′)-Diaminomethyl,(P,P′)-Ferrocenyl Ligands: Influence of tert-Butyl Groups on Ferrocene Backbone Conformation

et al. 2015

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Hexasubstituted hybrid tetradentate (N,N′,P,P′)-ferrocenes bearing phosphino and aminomethyl groups, plus hindering tert-butyl moieties, were synthesized by using two different strategies: a "diverging" synthesis involving successive functionalization of preformed di-tert-butylated ferrocene and a "converging" assembly of the species from appropriately substituted cyclopentadienyl rings. While the new cyclopentadienyl salts formed are of interest, their assembly with iron dichloride used as a "converging" way to produce tetradentate ferrocene ligands presented several drawbacks. Conversely, the synthesis of new tert-butylated (aminomethyl)ferrocene derivatives was found convenient to further form (N,N′)-aminomethyl,(P,P′)-tert-butylated-ferrocenyl diphosphines by N-directed ortho-metalation. The novel N 2didentate and N 2 P 2 -tetradentate tert-butylated ferrocene compounds were all synthesized in good to high yields (48−96%) and tolerated aryl, alkyl, and heteroaryl phosphino groups as substituents on nitrogen and phosphorus atoms. They were characterized by X-ray diffraction and multinuclear NMR ( 1 H, 13 C, 31 P, 15 N). We observed the conformation control provided to rac-(N,N′)-diaminomethyl-(P,P′)-tert-butylated-ferrocenyldiphosphines with in particular the systematic near-eclipsed conformation of aminomethyl groups. This conformation is at the origin of the unexpected formation at RT of a zwitterionic cyclopalladate from an (aminomethyl)ferrocene derivative, arising from intramolecular Cp-proton transfer to the proximate free amino group by simple C−H activation reaction in the presence of palladium dichloride.

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Transfer hydrogenation with a ferrocene diamide ruthenium complex

Abstract: The use of a 1,1'-ferrocenediamide ruthenium complex as a mediator for base-free transfer hydrogenation is reported. Ketones were transformed to their respective alcohols at room temperature in 36-99% conversions with turnover frequencies up to 339 h(-1).

Cited by 15 publications

References 29 publications

Reactivity and Properties of Metal Complexes Enabled by Flexible and Redox-Active Ligands with a Ferrocene Backbone

Reactivity and Properties of Metal Complexes Enabled by Flexible and Redox-Active Ligands with a Ferrocene Backbone

Investigation of the Electronic Structure of Mono(1,1′-Diamidoferrocene) Uranium(IV) Complexes

Converging and Diverging Synthetic Strategies to Tetradentate (N,N′)-Diaminomethyl,(P,P′)-Ferrocenyl Ligands: Influence of tert-Butyl Groups on Ferrocene Backbone Conformation

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