Hendrikus C L Abbenhuis

Hendrikus C L Abbenhuis
Hybrid Catalysis BV

PhD

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74
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Publications

Publications (74)
Article
Full-text available
p>POSS (polyhedral oligomeric silsesquioxanes) nanotechnology was applied for preparation of efficient Ni catalysts for hydrogen production through autothermal reforming of methane (ATR of CH<sub>4</sub>). The novel metal-POSS precursor [Nickel (II) ‒ HeptaisobutylPOSS (C<sub>4</sub>H<sub>9</sub>)<sub>7</sub>Si<sub>7</sub>O<sub>9</sub>(OH)O<sub>2</...
Article
Full-text available
Using XPS, BET, XRD, TG-DTA, HRTEM-EDX, TPR and UV-Vis Diffuse Reflectance spectroscopic methods the electronic, redox and structural properties of Mn-Na-W/SiO2 catalysts prepared by the incipient wetness impregnation method and mixture slurry method were studied in detail. Since POSS nanotechnology (POSS = polyhedral oligomeric silsesquioxanes) ha...
Article
The paper presents data on the development of catalytic materials with improved characteristics for catalytic membrane reactors of autothermal reforming of methane (ATR of CH4) obtained in the frame of the International collaborative project DEMCAMER – Design and Manufacturing of Catalytic Membrane Reactors by developing new nano-architectured cata...
Patent
Polyhedral oligomeric silsesquioxanes (POSS) linked ligand of the general formula (I) L[(R1a)n-1(SiO1,5)nR2a]k[(R1b)n-1SiO1,5)nR2b]l[(R1c)n-1SiO1,5)nR2c]m (I) in which (R1a,b,c)n-1(SiO1,5)n is a polyhedral oligomeric silsesquioxanes (POSS) with n=4, 6, 8, 10, 12, 14, 16 or 18 and R1a, R1b, R1c is each independently selected from the group consist...
Patent
A method to form a urethane material, the method comprises blending and reacting at least one isocyanate, at least one isocyanate reactive compound and a metallized polyhedral oligomeric silsesquioxane to provide said urethane material, the metallized polyhedral oligomeric silsesquioxane is a dimeric structure with general formula wherein M repre...
Article
The chemistry of atmospheric pressure chemical vapor deposition (APCVD) processes is believed to be complex, and detailed reports on reaction mechanisms are scarce. Here, the authors investigated the reaction mechanism of monobutyl tinchloride (MBTC) and water during SnO2 thin film growth using x-ray photoelectron spectroscopy (XPS) and transmissio...
Article
Silica cocoons are synthesized via a cooperation of hexagonal P123 micelles and O/W emulsions. These silica cocoons are closed on one side but open on another side. The wall of these silica cocoons is hierarchically constructed by hexagonally ordered channels, which is produced by the aggregation of P123 micelles onto the emulsion droplets while th...
Patent
Full-text available
A synthetic process for polyhedral oligomeric silsesquioxanes (POSS) and polyhedral oligomeric silicates (POS) produces silanol and siloxide molecules containing both olefinic groups and alkyl or aromatic groups. Olefin-bearing POSS silanol/siloxides are derivatized into a variety of chemical species while retaining the ability to further derivatiz...
Patent
Full-text available
Metallized polyhedral oligomeric silsesquioxanes and metallized polyhedral oligomeric silicates are used as cure promoters, catalysts, and alloying agents for the reinforcement of polymer microstructures, including polymer coils, domains, chains, and segments, at the molecular level. Because of their tailorable compatibility with polymers, polyhedr...
Article
The terdentate aryldiamine ligand in the aryltantalum(V) alkylidene complex [TaCl2{C6H3(CH2NMe2)2-2,6}(CHBut)] (1) controls alkylidene reactivity in a range of metal-mediated Wittig reactions. An X-ray diffraction study of (1) shows that the hexacoordinate tantalum centre has a very irregular ligand array in which the aryldiamine ligand adopts a ne...
Article
A stereoselective C-H activation reaction of a NMe group of [Ta{C6H4CH(Me)NMe2−2}-(CH2Ph)2Cl2 (1b) affords toluene and a species which was isolated as the new pentagonal bipyramidal Ta(V) tetrahydrofuran (THF) adduct [Ta{C6H4(CH(Me)N(Me)CH2)-2}(CH2Ph)Cl2- (THF)] (2). The chirality of the arylamine leads to a single structurally characterized diaste...
Article
Microporous, silica-supported metal oxides with a very narrow pore size distribution around 0.6 nm diameter, typical surface areas ranging from 350 to 700 m2/g, and loadings of well-dispersed metal oxide (up to w = 10% of metal) result from the controlled calcination of silsesquioxane metal complexes. A versatile new methodology is envisioned that,...
Patent
Full-text available
Metallized nanostructured chemicals are incorporated at the molecular level as alloying agents for the reinforcement of polymer microstructures, including polymer coils, domains, chains, and segments. Direct blending processes are effective because of the tailorable compatibility of the metallized nanostructured chemicals with polymers.
Article
The polyhedral oligomeric silsesquioxane trisilanolate vanadium(V) complex 1 efficiently catalyzes oxidations at room temperature using cumyl hydroperoxide as the terminal oxidant. Sulfoxidations and N-oxidations have been carried out yielding the corresponding products in good yields. The addition of a Lewis base as a coligand can markedly affect...
Article
Super-microporous organosilica with bridging ethylene and pendant vinyl groups has been synthesized by assembling predefined nanobuilding block polyhedral oligomeric silsesquioxanes (POSS) with nonionic surfactant Brij-76 as the template. The material shows wormhole-like super-micropores with uniform size of 1.9 nm, high BET surface area of 872 m2...
Article
Mesoporous silica-supported chiral Mn(salen) catalysts were prepared and evaluated in the heterogeneous asymmetric epoxidation of β-methylstyrene with NaClO as an oxidant. Homogeneous and immobilized Mn(salen) catalysts exhibit similar cis/trans ratios and ee values when trans-substrate is used but different cis/trans ratios and ee values when cis-...
Article
Fe/SiO2 catalysts have been prepared by two different sol–gel methods, cogelation and dissolution. The cogelation and dissolution preparative methods lead to xerogels with fundamentally different pore width distributions. The nature of the iron species obtained has been examined in detail by UV–visible and Mössbauer spectroscopy, and magnetic, tran...
Article
Organo-bridged silsesquioxane titanates for heterogeneous catalytic epoxidation with aqueous hydrogen peroxide were synthesized through the acid-catalyzed hydrolysis and co-condensation of organotrialkoxysilane monomers and alpha,omega)-bis(trialkoxysilyl) alkane cross-linkers in ethanol-water solution, with subsequent titanium grafting. These hybr...
Article
Gerundete Formen: Polyedrische oligomere Silsesquioxane (POSS), die zu den kleinsten hybriden Nanobausteinen gehören, wurden zu einem multifunktionellen hierarchischen mesoporösen Hybridmaterial verwoben, und zwar durch Coassoziation und Kondensation der POSS-Verbindung um Micellen aus dem Blockcopolymer P123 und anschließende Freisetzung des Porog...
Article
A novel interfacial hybrid epoxidation catalyst was designed with a new immobilization method for homogeneous catalysts by coating an inorganic support with an organic polymer film containing active sites. The titanium silsesquioxane (TiPOSS) complex, which contains a single-site titanium active center, was immobilized successfully by in-situ copol...
Article
This paper deals with the study of the combustion properties of dimeric and oligomeric Al-and Zn-isobutyl silsesquioxane (POSS)/polypropylene (PP) composites, in comparison with neat PP and PP/octaisobutyl POSS.The presence of Al-POSS leads to a decrease in combustion rate with respect to PP, resulting in a decrease of Heat Release Rate (−43% at 10...
Article
Dimeric and oligomeric Al and Zn-containing isobutyl silsesquioxanes (POSS) were studied to investigate their thermal stability both in inert and oxidant atmosphere, by means of Differential Scanning Calorimetry (DSC) and thermogravimetric analyses (TGA).Thermo-oxidative degradation leads to an important solid residue yield, as a consequence of the...
Article
The synthesis of novel chiral tri- and bidentate phosphites 2, 5, 6 and 8, derived from incompletely condensed silsesquioxane backbones and binaphthol, is described. These compounds can be obtained in good yield and are characterized by multinuclear NMR spectroscopy, mass spectrometry and elemental analyses. The complexation with [Rh(cod)2]BF4 has...
Article
The chemistry of polyhedral oligomeric silsesquioxanes (POSS) has taken a tremendous leap over the past decade. New synthetic approaches have been developed, and new complexes based on elements throughout the periodic table have been synthesized and applied in catalytic processes such as alkene epoxidation, Oppenauer oxidation, alkene polymerizatio...
Article
Silsesquioxanes are employed as ligand backbones for the synthesis of novel phosphite compounds with 3,3′-5,5′-tetrakis(tert-butyl)-2,2′-dioxa-1,1′-biphenyl substituents. Both mono- and bidentate phosphites are prepared in good yields. Two types of silsesquioxanes are employed as starting materials. The monophosphinite 1 and the monophosphite 2 are...
Article
The incompletely condensed silsesquioxane disilanol (c-C5H9)7Si7O9(OH)2OSiMePh2 has been used as a backbone for the synthesis of the diphosphinite ligand (c-C5H9)7Si7O9(OPPh2)2OSiMePh2 (1), based on a silsesquioxane framework. By reaction with black selenium, the corresponding selenide (2) was obtained, showing a JSe-P value of 815 Hz in the 31P NM...
Article
A straightforward three-step synthetic route is followed to obtain nanostructured silsesquioxane based monophosphite compounds 1–3, which we named POSSphites. These compounds, derived from (c-C5H9)7Si7O9(OH)3 and commercially available phenol derivatives, differ mainly in the steric bulk around the phosphorus atom. Preliminary results in the rhodiu...
Article
Calcination of silsesquioxane mixtures of (c-C5H9)7Si7O9(OH)3, 1, (c-C5H9)7Si7O12Fe(CH3)2N(CH2)2N(CH3)2, 2, and (c-C5H9)7Si7O9(OSiMe3)O2CrO2, 3, led to microporous amorphous bimetallic Fe–Cr–Si–O materials with different Fe∶Cr ratios. A set of complementary characterisation techniques including N2 physisorption, XRD, XPS, RS, IR, HRTEM and Mössbaue...
Article
Katalytische Ensembles für die Alkenepoxidierung mit wässrigem Wasserstoffperoxid sind nun zugänglich. Die Herstellung solcher Systeme gelingt durch Pfropfung robuster Titansilsesquioxan-Aktivzentren an Dimethylsiloxanpolymere (siehe Bild) und nachfolgende Quervernetzung zu dreidimensionalen Polymeren.
Article
Calcination of mixtures of (c-C5H9)7Si7O9(OH)3, 1, and (c-C5H9)7Si7O12Fe(tmeda), 2 (tmeda = N,N,N‘,N‘-tetramethylethylenediamine), led to microporous amorphous Fe−Si−O materials with adjustable iron content in the range 1−11 wt %. A set of different complementary techniques including N2 physisorption, XRD, XPS, DRUV−vis, RS, IR, HRTEM, and Mössbaue...
Article
Catalytic ensembles suitable for alkene epoxidation with aqueous hydrogen peroxide are now accessible. They are made by grafting robust titanium silsesquioxane sites onto dimethylsiloxane polymers (see picture) followed by cross-linking to three-dimensionally netted polymers.
Article
Microporous amorphous metallosilicates designated as Mg−Si−O and Al−Si−O, with a very narrow pore size distribution around 6 Å diameter, typical surface areas ranging from 350 to 650 m2/g, and loadings of well-dispersed metal oxide (up to about 10 wt % metal) result from the controlled calcination of magnesium and aluminum silsesquioxane complexes...
Article
The reaction of a silsesquioxane trisilanol with methylmagnesium chloride leads to an unprecedented tetranuclear magnesium silsesquioxane complex 1 in high yield. The crystal structure shows an unusually short Mg-Cl bond, indicative of an electron-deficient magnesium atom; 1 has been used as transmetalation agent for the synthesis of metal silsesqu...
Article
“Conjunct oligomerization” of propylene or the isopentane–propylene alkylation catalyzed by an excess of 95% sulfuric acid was performed in two consecutive steps. First di-isopropylsulfate was prepared by interaction of sulfuric acid with propylene. The ester was then either decomposed at room temperature in the presence of the 5–10 molar excess of...
Article
Metal-containing silsesquioxane derivatives provide new catalysts with both homogeneous and heterogeneous applicability. The steric and electronic properties of silsesquioxane silanolate ligands render metal centers more Lewis acidic than conventional alkoxide or siloxide ligands do. This concept has been exploited in newly developed catalysts for...
Article
The cuboctameric hydroxysilsesquioxane (c-C5H9)7Si8O12(OH) (2), obtained after hydrolysis of (c-C5H9)7Si8O12Cl (1), and triphenylsilanol have been applied as model supports for silica-grafted olefin polymerization catalysts. The ligands were introduced on group 4 metals by either chloride metathesis or protonolysis. Treatment of Cp‘ ‘MCl3 (M = Ti,...
Article
Protolysis of alkylaluminum compounds with silsesquioxanes is an efficient procedure to synthesize both Lewis and Brønsted acidic aluminosilsesquioxanes. Treatment of AlEt3 with (c-C5H9)7Si7O9(OH) 3 and (c-C5H9)7Si7-O 9(OSiMe3)(OH)2 gives the corresponding Lewis acidic aluminosilses-quioxanes, {[(c-C5H9)7Si7O 12]Al}n (l) and [(c-C5H9)7Si7O11 (OSiMe...
Article
The controlled calcination of the chromium containing polyhedral oligosilsesquioxane (c-C5H9)7Si7O9- (OSiMe3)O2CrO2, 3b, monitored by MS analysis of the evolved gases and thermogravimetry measurements, led to the formation of a microporous Cr–Si–O amorphous mixed oxide containing 10.2 wt.% of chromium. The textural properties of the material as wel...
Article
Beyond mere convenience: In large-scale industrial processes for alkene polymerization the essentially homogeneous metallocene/activator catalyst systems are heterogenized (example shown) to improve polymer properties. New mesoporous and organic catalyst supports and their application in this field of catalysis are described.
Article
Nicht einfach nur bequem: Für industrielle, in großem Maßstab durchgeführte Alkenpolymerisationen werden die homogenen, aus einem Metallocen und einem Aktivierungsagens bestehenden Katalysatoren heterogenisiert (im Bild ist ein Beispiel gezeigt), um die Polymereigenschaften zu verbessern. Neue mesoporöse und organische Katalysatorträger sowie deren...
Article
FTIR hydroxyl vibration bands in highly dealuminated zeolites could be unambiguously assigned to well defined hydroxyl clusters present at defect sites by the use of density functional calculations on incompletely condensed silasesquioxane complexes which, in addition, provided useful spectroscopic references.
Article
Die Heterogenisierung eines Titan(IV)-Silsesquioxankomplexes in einem MCM-41-Molekularsieb durch Einstellen der Polarität des MCM-41-Netzwerkes führt zu selbstorganisierten Materialverbänden (Kalottenmodell rechts), die sich als aktive, heterogene und somit wiederverwendbare Katalysatoren für die Alken-Oxidation in flüssiger Phase eignen.
Article
This paper describes a spectroscopic study of the heterogenisation of a novel liquid-phase epoxidation catalyst, a titanium(IV) silsesquioxane complex. Its immobilisation is performed exclusively via a straightforward adsorption of the homogeneous catalyst, i.e. the metal complex, in the pores of an MCM-41 host material. Applying all-silica MCM-41...
Article
The reaction of partially condensed silasesquioxanes of the type [(R7Si7O9)-Si-1(OH)(2)(OR2)] (R-1 = c-C5H9, C-C6H11; R-2 = H, SiMe3) with either [Pt(dppe)(CO3)] or [Pt(dppe)Cl-2]/Ag2O leads to the formation of [(R7Si7O9)-Si-1(OR2)O2Pt(dppe)], crystallographically characterised for R-1 = c-C5H9; R-2 = SiMe3, providing unprecedented routes to late t...
Article
Treatment of the silanol (c-C5H9)7Si8O12(OH) with Cp‘‘Ti(CH2Ph)3 (Cp‘‘ = 1,3-C5H3(SiMe3)2) or TiCl4 selectively affords the mono(silsesquioxane) complexes Cp‘‘[(c-C5H9)7Si8O13]Ti(CH2Ph)2 (1) and [(c-C5H9)7Si8O13]TiCl3 (2), respectively, while with M(CH2Ph)4 (M = Ti, Zr, Hf) mixtures of products were obtained. When the disilanol (c-C5H9)7Si7O9(OSiMe...
Article
The cuboctameric silsesquioxane silanol (c-C5H9)7Si8O12(OH) has been applied as a model support for silica-grafted olefin polymerization catalysts. Complexes of the type Cp‘‘[(c-C5H9)7Si8O13]TiX2 (Cp‘‘ = 1,3-C5H3(SiMe3)2; X = Cl, CH2Ph) form active α-olefin polymerization catalysts.
Article
The heterogenization of a titanium(IV) silsesquioxane complex in an MCM-41 molecular sieve, by tailoring the polarity of MCM-41, results in self-assembled materials (see the space-filling model on the right) that are active, truly heterogeneous, and recyclable catalysts for liquid-phase alkene epoxidation.
Article
A bimetallic chromium siloxane complex, [Cr(O)2{(OSiPh2)2O}]2 (1), containing a unique 12-membered metallacyclic [-O−Si−O−Cr−O−Si−]2 fragment in a pseudo chair type conformation, results from the reaction of 1,1,3,3-tetraphenyldisiloxane-1,3-diol with chromium(vi) oxide.
Article
Active catalysts for the epoxidation of alkenes by tert-butyl hydroperoxide are provided by silasesquioxane titanium(IV) derivatives; a non-leaching catalyst, not prone to irreversible protic cleavage of its siloxy functions by the oxidizing agent, contains a terdentate silasesquioxane ligand.
Article
A route to enantiopure heteroleptic ruthenocenyl derivatives has been found; the diastereoselective addition of MeLi to (R)-CyCH(Me)N(Me)CHC5H4 (de = 74%), followed by a transmetalation reaction with either [Cp*Ru(μ3-Cl)]4 or [(p-cymene)RuCl2]2/KPF6, afforded the heteroleptic complexes (S,R)-[Cp*Ru(η5-C5H4CH(Me)N(Me)CH(Me)Cy)], 6, or (S,R)-[(p-cyme...
Article
A highly active, genuinely heterogeneous catalyst for liquid-phase Diels–Alder reactions of enones results from the silanol centred modification of an incompletely condensed silasesquioxane with trimethylaluminium, the resulting catalytic material being a gel that contains aluminium(III) siloxy functions (Al–O–Si) which are incorporated in a well d...
Article
The technical mixture ''phobane'', containing the two isomers 9-phospha-9H-bicyclo[3.3.1]-nonane (3a) and 9-phospha-9H-bicyclo[4.2.1]nonane (3b) in a similar to 2:1 ratio was reacted with N,N-dimethyl-(S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (4) in acetic acid. The clean amine substitution product is the new chiral biphosphine 5. When...
Article
Optical active 6-(dialkylamino)fulvenes, derived from (R)-(1-phenylethyl)amine, (R)-(1-cyclohexylethyl)amine, and O-methylephedrine, respectively, were used to prepare chiral cyclopentadienyl synthons. The addition of MeLi to these fulvenes, affording the corresponding dialkyl(1-cyclopentadienylethyl)amines, was found to occur with high diastereose...
Article
New cycloruthenated complexes can be obtained by transmetalation of [(eta6-arene)RuCl2]2 (arene = C6H6 or i-PrC6H4Me-1,4) with several mercury- or zinc-metalated [ (N,N-dimethylamino)methyl]benzene derivatives. Intramolecular C-H activation using these amines with [eta6-C6H6)RuCl2]2 affords the same cycloruthenated complexes though in lower yield....
Article
The 1:1 reaction of TaCl2{C6H3(CH2NMe2)2-2,6}(=CH-t-Bu) with neopentylzinc chloride affords the bimetallic complex TaCl2{C6H3(CH2NMe2)2-2,6}(mu-C-t-Bu) (mu-ZnCI) (2) in high yield. Crystals of 2 belong to the space group P2(1)2(1)2(1) with a = 9.725(2) angstrom, b = 10.436(2) angstrom, c = 20.766(3) angstrom, Z = 4, M(r) = 613.11, V = 2107.5(7) ang...
Article
Cyclometalated aryltantalum(V) complexes containing a five-membered Ta-C-C-C-N chelate ring can be prepared by transmetalation reactions. The 1:2 reaction of [Zn(C[sub 6]H[sub 4]CH[sub 2]NMe[sub 2]-2)[sub 2]] with TaCl[sub 5] affords [TaCl[sub 4](C[sub 6]H[sub 4]CH[sub 2]NMe[sub 2]-2)] (1a) in high yield. [TaCl[sub 4][l brace]C[sub 6]H[sub 4]CH(Me)...
Article
Cyclometalated aryltantalum(V) complexes containing a five-membered Ta-C-C-C-N chelate ring can be prepared by transmetalation reactions. The 1:2 reaction of [Zn(C[sub 6]H[sub 4]CH[sub 2]NMe[sub 2]-2)[sub 2]] with TaCl[sub 5] affords [TaCl[sub 4](C[sub 6]H[sub 4]CH[sub 2]NMe[sub 2]-2)] (1a) in high yield. [TaCl[sub 4][l brace]C[sub 6]H[sub 4]CH(Me)...
Article
An asymmetrically bridging aryldiamine ligand is the salient structural feature of the binuclear complex 1, formed from the corresponding alkylidenetantalum complex and neopentylzinc chloride with elimination of neopentane. The structural data indicate that the Ta-C-Zn bridge lies midway in character between a three-center two-electron bond and a c...
Article
A stereoselective C-H activation reaction of a NMe group of the Ta(V) compound (I) affords toluene and the new pentagonal pyramidal Ta(V) THF adduct (III) (space group P1, Z=4).
Article
[Ta(CH2Ph)2Cl3] reacts with [Zn{C6H4CH(R)NMe2-2}2](R = H, Me) to afford the new tantalum(V) complexes [Ta{C6H4CH(R)NMe2-2}(CH2Ph)2Cl2] in high yield; these complexes contain a five-membered [graphic omitted] chelate ring, in both the solid state and in solution, through intramolecular co-ordination of a trialkylamine ligand.

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