Easily Immobilized Di- and Tetraphosphine Linkers:  Rigid Scaffolds that Prevent Interactions of Metal Complexes with Oxide Supports

Yang, Yuan; Beele, Björn B.; Blümel, Janet

doi:10.1021/ja800541c

Cited by 54 publications

(34 citation statements)

References 21 publications

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“…[18] Additional proof for the immobility of ferrocenium salts on the silica surface has been derived from the following series of experiments. [18] Additional proof for the immobility of ferrocenium salts on the silica surface has been derived from the following series of experiments.…”

Section: Visualization Of Translationalm Obilitymentioning

confidence: 99%

Adsorption of Metallocenes on Silica

Cluff

Blümel

2016

Chemistry A European J

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The adsorption of the metallocenes ferrocene, doubly deuterated ferrocene, cymantrene and nickelocene, as well as molybdenum hexacarbonyl, proceeds in the absence of a solvent. Large single pieces of silica gel were placed in contact with the solid metallocenes and the adsorption process was visualized on a macroscopic scale and the maximal loadings were determined. H, H, and C solid-state NMR studies confirmed fast isotropic reorientation of the surface-adsorbed metallocene molecules within the pores of the silica. All prevalent anisotropic solid-state interactions were averaged out. The solid diamagnetic and paramagnetic materials were amenable to measurements with a standard solution NMR instrument. All metallocenes adsorbed in a monolayer. In the case of ferrocene and cymantrene, different C MAS signals were obtained for the cyclopentadienyl ring carbon nuclei and assigned to one ring interacting with the surface and one ring pointing away from it. The relative adsorption strengths of ferrocene on different silica supports, nanotubes, and activated carbon were determined by a novel straightforward method recording the desorption temperature. The reversibility of adsorption has been demonstrated by competition experiments using ferrocene, doubly deuterated ferrocene, and cymantrene. Adsorbed nickelocene could be reduced to small Ni aggregates on the surface and the catalytic activity of the resulting material for the cyclotrimerization of phenylacetylene was proven.

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Section: Visualization Of Translationalm Obilitymentioning

confidence: 99%

Adsorption of Metallocenes on Silica

Cluff

Blümel

2016

Chemistry A European J

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“…This might either happen by modification of the ligand, allowing a strong interaction with a support of opposite charge or by direct metal support interactions ( figure 4a,b). The advantage of immobilization by the ligand is that the method can be applied to catalysts neutral on the ligand and that leaching might be diminished, as the catalyst can change oxidation state or charge during catalysis (Yang et al 2008).…”

Section: Other Materials In Single-atom Active Site Heterogeneous Catmentioning

confidence: 99%

Single-atom active sites on metal-organic frameworks

et al. 2012

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Single-site heterogeneous catalysis has been recently accepted as a novel branch of heterogeneous catalysis. Catalysts with single-atom active sites (SAHCs) allow the design and fine-tuning of the active moiety, and can potentially combine the advantages of heterogeneous and homogeneous catalysis. This study illustrates how porous metalorganic frameworks (MOFs) can be synthesized with homogeneous distribution of SAHCs. The catalytic potential of MIXMOFs is shown. A short overview of catalysis with mesoporous silica materials is described to demonstrate their importance in SAHC.

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“…[21][22][23][25][26][27][28][29][30] For one, they are unwanted byproducts of phosphine chemistry, for example, in the field of immobilizedc atalysts. [25][26][27][28] They are encountered when Rh catalysts are tethered to as upport by monodentate or chelating phosphine linkers incorporating alkyl chains, [25] and by tetraphosphines with a rigid tetraphenylelement scaffold [26] because Rh catalyzes phosphine oxidation. But phosphine oxides are also found when Pd/Cu Sonogashira [27] and Ni catalysts are immobilized with biand tridentate phosphine linkers.…”

Section: Introductionmentioning

confidence: 99%

Structures and Dynamics of Secondary and Tertiary Alkylphosphine Oxides Adsorbed on Silica

Kharel

Cluff

Bhuvanesh

et al. 2019

Chemistry An Asian Journal

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The three secondary phosphine oxides[ CH 2 = CH(CH 2 ) 4 ] 2 HPO (1), [CH 2 = CH(CH 2 ) 5 ] 2 HPO (2), and [CH 2 = CH(CH 2 ) 6 ] 2 HPO (3), and two diphosphine dioxides, {[CH 2 = CH(CH 2 ) 6 ] 2 PO(CH 2 ) 7 } 2 (4)a nd {[CH 2 = CH(CH 2 ) 6 ] 2 PO(CH 2 ) 4 } 2 (5), incorporating long methylene chains, are described. The single crystal X-ray structures of 1, 2,a nd 5 have been determined. The phosphine oxides 3, 4,a nd 5 have been ad-sorbedo ns ilica in submonolayer quantities to give 3a-5a. The 1 H, 13 C, and 31 Ps olid-state NMRs pectra of polycrystalline 3-5 have been analyzeda nd compared with those of 3a-5a.T he changes of the solid-state NMR characteristics upon adsorption and the surfacem obilities of the phosphine oxides are discussed.[a] Dr.

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Easily Immobilized Di- and Tetraphosphine Linkers: Rigid Scaffolds that Prevent Interactions of Metal Complexes with Oxide Supports

Cited by 54 publications

References 21 publications

Adsorption of Metallocenes on Silica

Adsorption of Metallocenes on Silica

Single-atom active sites on metal-organic frameworks

Structures and Dynamics of Secondary and Tertiary Alkylphosphine Oxides Adsorbed on Silica

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