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

The three secondary phosphine oxides [CH₂=CH(CH₂)₄]₂HPO ( 1 ), [CH₂=CH(CH₂)₅]₂HPO ( 2 ), and [CH₂=CH(CH₂)₆]₂HPO ( 3 ), and two diphosphine dioxides, {[CH₂=CH(CH₂)₆]₂PO(CH₂)₇}₂ ( 4 ) and {[CH₂=CH(CH₂)₆]₂PO(CH₂)₄}₂ ( 5 ), incorporating long methylene chains, are described. The single crystal X‐ray structures of 1 , 2 , and 5 have been determined. The phosphine oxides 3 , 4 , and 5 have been adsorbed on silica in submonolayer quantities to give 3 a – 5 a . The ¹H, ¹³C, and ³¹P solid‐state NMR spectra of polycrystalline 3 – 5 have been analyzed and compared with those of 3 a – 5 a . The changes of the solid‐state NMR characteristics upon adsorption and the surface mobilities of the phosphine oxides are discussed.     

Modification of Silica by Liquid Polybutadienes Containing Alkoxysilane Groups

Summary : The present work describes a method to modify the surface of silica, reducing its polar character and making it compatible and dispersible into hydrocarbon based elastomers. A liquid low molar mass polybutadiene (PB) was grafted with mercaptopropyltrimethoxysilane (MPTS) via radical addition of the thiol group to the double bonds. The silanized PB was reacted with silica via thermal condensation with its silanol groups. ²⁹Si NMR spectra showed that the condensation reaction of the trifunctional silane involved one or two alkoxy groups, while the third alkoxy group remained unreacted, probably for steric reasons. The characterization of the functionalized silica particles was performed by contact angle measurements and TGA analysis.     

Well‐Defined Silica‐Supported Mo–Alkylidene Catalyst Precursors Containing One OR Substituent: Methods of Preparation and Structure–Reactivity Relationship in Alkene Metathesis

Silica supports : Well‐defined silica‐supported Mo–alkylidene complexes containing one alkoxy/aryloxy substituent are selectively obtained by grafting onto silica either well‐defined molecular bis(alkoxy) or alkoxyamido complexes (see scheme). These silica‐supported complexes are highly efficient catalyst precursors for the metathesis of acyclic alkenes. However, they display poor performances in ring‐closing metathesis reactions, possibly due to the relatively large siloxy ligand (silica) inducing a greater rigidity.

     

Revealing the Fine Details of Functionalized Silica Surfaces by Solid‐State NMR and Adsorption Isotherm Measurements: The Case of Fluorinated Stationary Phases for Liquid Chromatography

The structural and chromatographic characterization of two novel fluorinated mesoporous materials prepared by covalent reaction of 3‐(pentafluorophenyl)propyldimethylchlorosilane and perfluorohexylethyltrichlorosilane with 2.5 μm fully porous silica particles is reported. The adsorbents were characterized by solid state ²⁹Si, ¹³C, and ¹⁹F NMR spectroscopy, low‐temperature nitrogen adsorption, elemental analysis (C and F), and various chromatographic measurements, including the determination of adsorption isotherms. The structure and abundance of the different organic surface species, as well as the different silanol types, were determined. In particular, the degree of so‐called horizontal polymerization, that is, Si‐O‐Si bridging parallel to the silica surface due to the reaction, under “quasi‐dry” conditions, of trifunctional silanizing agents with the silica surface was quantified. Significant agreement was found between the information provided by solid‐state NMR, elemental analysis, and excess isotherms regarding the amount of surface residual silanol groups, on the one hand, and the degree of surface functionalization, on the other. Finally, the kinetic performance of the fluorinated materials as separation media for applications in near‐ultrahigh‐performance liquid chromatography was evaluated. At reduced velocities of about 5.5 (ca. 600 bar backpressure at room temperature) with 3 mm diameter columns and toluene as test compound, reduced plate heights on the order of 2 were obtained on columns of both adsorbents.     

Synthesis and Properties of Hyperbranched Polyimides Combined with Silica

Summary: The novel hyperbranched polyimide - silica hybrid materials containing theoretically 16 wt% of an inorganic phase were prepared via a sol-gel process. An amine terminated polyimide precursor (hyperbranched polyamic acid) was prepared from commercially available monomers 4,4′,4″-triaminotriphenylmethane and 4,4′-oxydiphthalic anhydride in molar ratio 1:1. Tetramethoxysilane and/or 3-glycidoxypropyltrimethoxysilane (also used as a coupling agent) were used as silica precursors. During thermal exposition the polyimide precursor was transformed to hyperbranched polyimide and hydrolyzed alkoxy groups reacted mutually to form silica. The final products were self-standing films, whose structure was characterized by using IR and ¹³C and ²⁹Si solid state NMR spectroscopy. The influence of the amount of silica and/or coupling agent on their structure and thermal properties was described.     

Coulombic Basis for Relative Hydrogen-Bonding Basicities and Conformational Energies of Tertiary Amine Oxides and Phosphine Oxides

The structures, energies, and natural atomic charges of 2-dimethylaminophenol oxide, 2-Me₂N-(O)C₆H₄OH, and 2-dimethylphosphinylphenol, 2-Me₂P(O)C₆H₄OH, in three different conformations were computed at the ab initio MP2/6-31G* level. Computed natural charges indicate distributions of electron density in amine oxides and phosphine oxides that are quite different from what is normally assumed on the basis of the formal charges in the usual representations of these compounds. The charges on nitrogen and phosphorus in these compounds are typically computed to be approximately zero on nitrogen and +2 on phosphorus, and the oxygen is considerably more negative in the phosphine oxide than in the amino oxide. Electronegativity differences thus play a larger role and formal charges a smaller one in determining atomic charges in these compounds than is generally believed. Despite the more negative oxygen in phosphine oxides, amine oxides are computed to be considerably more basic when participating in hydrogen bonding. Calculations treating the computed natural charges on these six conformations as point charges for classical approximations of the coulombic energies support the idea that the quantum mechanically computed relative energies are largely determined by coulombic interactions.     

Labeling and Probing the Silica Surface Using Mechanochemistry and 17O NMR Spectroscopy**

In recent years, there has been increasing interest in developing cost-efficient, fast, and user-friendly ¹⁷O enrichment protocols to help to understand the structure and reactivity of materials by using ¹⁷O NMR spectroscopy. Here, we show for the first time how ball milling (BM) can be used to selectively and efficiently enrich the surface of fumed silica, which is widely used at industrial scale. Short milling times (up to 15 min) allowed modulation of the enrichment level (up to ca. 5 %) without significantly changing the nature of the material. High-precision ¹⁷O compositions were measured at different milling times by using large-geometry secondary-ion mass spectrometry (LG-SIMS). High-resolution ¹⁷O NMR analyses (including at 35.2 T) allowed clear identification of the signals from siloxane (Si−O−Si) and silanols (Si−OH), while DNP analyses, performed by using direct ¹⁷O polarization and indirect ¹⁷O{¹H} CP excitation, agreed with selective labeling of the surface. Information on the distribution of Si−OH environments at the surface was obtained from 2D ¹H−¹⁷O D-HMQC correlations. Finally, the surface-labeled silica was reacted with titania and using ¹⁷O DNP, their common interface was probed and Si−O−Ti bonds identified.     

A novel green template for the synthesis of mesoporous silica

Mesoporous pure silicas and functionalized silica with a narrow pore size distribution centered at 3.8 nm were prepared by a novel template, amphiphilic dendritic polyglycerol. The resulting silica materials were characterized by electron microscopy; nitrogen adsorption; (1)H, (13)C, and (29)Si solid-state cross-polarization magic-angle spinning NMR spectroscopy. It was shown that the template could be completely removed from the pure and functionalized silica in an environmentally friendly way by means of a simple water extraction procedure. Furthermore, it was shown that these materials could be easily functionalized, for example, by employing aminopropyl groups. Thus, a new environmentally friendly pathway to this fascinating class of silica material has been opened.     

High‐Temperature Chlorination‐Reduction Sequence for the Preparation of Silicon Hydride Modified Silica Surfaces

A general method for the functionalization of silica surfaces with silicon hydride (Si–H) groups is described for four different preparations of silica. The silica surface is reduced in a two‐step chlorination–reduction procedure within a simple gas‐flow system at high temperatures. After initial dehydroxylation of the silica surface, silicon chloride groups are formed by the reaction with thionyl chloride. The chlorination activates otherwise inaccessible surface siloxane moieties. A high silicon–hydride surface concentration results from the subsequent reduction of the chlorinated surface with hydrogen. The physical properties of the resulting silica are analyzed using scanning electron microscopy, as well as dynamic light scattering and Brunauer–Emmet–Teller measurements. The chlorination–reduction sequence has no significant impact on the structure, surface area and mesopore size of the silica materials used. The surface of the materials is characterized by diffuse reflectance infrared Fourier transform (DRIFT) and ²⁹Si CP/MAS NMR spectroscopy. The silicon–hydride groups are mostly of the ‐type. The use of high temperatures (>800 °C) results in the condensation of internal and surface silanol groups. Therefore, materials with both a fully condensed silica matrix as well as a surface free of silanol groups are obtained. The materials are ideal precursors for further molecular silica surface modification, as demonstrated with a ferrocene derivative.     

各种孔结构活性炭吸附苯、环己烷、正戊烷和正己烷的~1H和~(13)C NMR研究

~1H和~(13)C NMR研究证明被吸附在不同孔结构活性炭中的烃类以毛细管凝聚和吸附在固体表面两种状态存在。链状烷烃平铺地吸附在固体表面。被吸附烃与活性炭表面酸性基团的质子交换在弛豫过程中起着重要作用。     

Preparations of Saturated N‐P‐N Type Secondary Phosphine Oxides and their Applications in Cross‐Coupling Reactions

A series of cyclohexane‐1,2‐diamine ( 3a – 3d ) and benzene‐1,2‐diamine derivatives ( 3e – 3h ) were pre‐ pared. Followed by hydrolysis, the reaction of 3a – 3c with PCl₃ successfully led to the formation of cor‐ responding metastable saturated heteroatom‐substituted secondary phosphine oxides (HASPO 4a – 4c ), a tautomer of the saturated heteroatom‐substituted phosphinous acid (HAPA). Whereas ambient‐stable diamine‐coordinated palladium complexes were obtained, HAPA‐coordinated palladium complexes were not successfully synthesized. The molecular structures of HASPO 4c , Pd(OAc)₂(3a) , PdBr₂(3b) and Pd(OAc)₂(3c) and [Cu(NO₃)(3d)⁺][NO₃ ^? ] were determined by single‐crystal X‐ray diffraction method. Catalysis of in‐situ Suzuki‐Miyaura cross‐coupling reactions for aryl bromides and phenylboronic acid using diamine 3a as ancillary ligand showed that the optimized reaction condition at 60 °C is the combination of 2 mmol % 3a /3.0 mmol KOH/1.0 mL 1,4‐dioxane/1 mmol % Pd(OAc)₂. Moreover, moderate reactivity was observed when using aryl chlorides as substrates (supporting infor‐ mation). When diamine 3d was employed in Heck reaction, good tolerance of functional groups of aryl bromides were observed while using 4‐bromoanisole and styrene as substrates. The optimized condi‐ tion for Heck reaction at 100 °C is 3 mmol % 3d /3.0 mmol CsF/1.0 mL toluene/3 mmol % Pd(OAc)₂. In general, cyclohexane‐1,2‐diamine derivatives exhibited better catalytic properties than those of benzene‐1,2‐diamines.     

Spin‐Polarized Structures and Solid‐State NMR Spectroscopy of Paramagnetic Compounds

On an atomic scale and with high sensitivity, solid‐state NMR spectroscopy can provide information about the electronic spin density and coupling mechanisms in paramagnetic compounds. The picture shows how the hyperfine splitting collapses through relaxation. Insights into which compounds are suitable and which approximations have to be made are given.

     

Monometallic Ni0 and Heterobimetallic Ni0/AuI Complexes of Tripodal Phosphine Ligands: Characterization in Solution and in the Solid State and Catalysis

The tridentate chelate nickel complexes [(CO)Ni{(PPh₂CH₂)₃CMe}] ( 2 ), [(CO)Ni{(PPh₂CH₂CH₂)₃SiMe}] ( 6 ), and [Ph₃PNi{(PPh₂CH₂CH₂)₃SiMe}] ( 7 ), as well as the bidentate complex [(CO)₂Ni{(PPh₂CH₂)₂CMeCH₂PPh₂}] ( 3 ) and the heterobimetallic complex [(CO)₂Ni{(PPh₂CH₂)₂CMeCH₂Ph₂PAuCl}] ( 4 ), have been synthesized and fully characterized in solution. All ¹H and ¹³C NMR signal assignments are based on 2D‐NMR methods. Single crystal X‐ray structures have been obtained for all complexes. Their ³¹P CP/MAS (cross polarization with magic angle spinning) NMR spectra have been recorded and the isotropic lines identified. The signals were assigned with the help of their chemical shift anisotropy (CSA) data. All complexes have been tested regarding their catalytic activity for the cyclotrimerization of phenylacetylene. Whereas complexes 2 – 4 display low catalytic activity, complex 7 leads to quantitative conversion of the substrate within four hours and is highly selective throughout the catalytic reaction.     

Unexpected Factors Affecting the Kinetics of Guest Molecule Release from Investigation of Binary Chemical Systems Trapped in a Single Void of Mesoporous Silica Particles

In this work, we present results for loading of well-defined binary systems (cocrystal, solid solution) and untreated materials (physical mixtures) into the voids of MCM-41 mesoporous silica particles employing three different filling methods. The applied techniques belong to the group of “wet methods” (diffusion supported loading – DiSupLo ) and “solvent-free methods” (mechanical ball-mill loading – MeLo , thermal solvent free – TSF ). As probes for testing the guest1-guest2 interactions inside the MCM-41 pores we employed the benzoic acid ( BA ), perfluorobenzoic acid ( PFBA ), and 4-fluorobenzoic acid ( 4-FBA ). The guests intermolecular contacts and phase changes were monitored employing magic angle spinning (MAS) NMR Spectroscopy techniques and powder X-ray diffraction (PXRD). Since mesoporous silica materials are commonly used in drug delivery system research, special attention has been paid to factors affecting guest release kinetics. It has been proven that not only the content and composition of binary systems, but also the loading technique have a strong impact on the rate of guests release. Innovative methods of visualizing differences in release kinetics are presented.     

Nanorods of Various Oxides and Hierarchically Structured Mesoporous Silica by Sol-Gel Electrophoresis

In this paper, we report the template-based growth of nanorods of oxides and hierarchically structured mesoporous silica, formed by means of a combination of sol-gel processing and electrophoretic deposition. Both single metal oxides (TiO₂) and complex oxides (Pb(Zr_0.52Ti_0.48)O₃) have been grown by this method. This method has also been applied to the growth of nanorods of mesoporous silica having an ordered pore structure, where the pores are aligned parallel to the long axis of the nanorod. Uniformly sized nanorods of about 125–200 nm in diameter and 10 m in length were grown over large areas with near unidirectional alignment. Appropriate sol preparation yielded the desired stoichiometric chemical composition and crystal structure of the oxide nanorods, with a heat treatment (500–700°C for 15–30 min) for crystallization, densification and any necessary pyrolysis.     

The Structure of (SCN)x: A Study Using Molecular and Solid‐State Density Functional Theory Calculations

A riddle solved! Despite its simple formula, the structure of the (SCN)_x polymer has remained elusive since its first synthesis in 1929. From energetics as well as NMR chemical shifts, based on DFT calculations, we have strong evidence that it is indeed a tangle of linear chains, made up from N‐linked S₂C₂N five‐membered rings.

     

Hydrogen Peroxide and Di(hydroperoxy)propane Adducts of Phosphine Oxides as Stoichiometric and Soluble Oxidizing Agents

Aqueous hydrogen peroxide is widely used as an oxidizing agent in industry and academia. Herein, the hydrogen peroxide adducts of phosphine oxides, [tBu₃PO ? H₂O₂]₂ and [Ph₃PO ? H₂O₂]₂ ? H₂O₂, are described. Additionally, the corresponding di(hydroperoxy)propane adducts R₃PO ? (HOO)₂CMe₂ (R=Cy, Ph) were synthesized and characterized. All adducts could be obtained as large single crystals suitable for structural characterization by X‐ray crystallography and solid‐state NMR spectroscopy. The di(hydroperoxy)propane adducts are soluble in organic solvents which enables oxidation reactions in one phase. As the adducts are solid and molecular, they can easily be applied stoichiometrically. No loss of oxidizing power occurs upon long‐term storage of the single crystals at room temperature or the powders at ?20 °C.