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31.
Anna G. Scott Diogo Alves Galico Isabel Bogacz Paul H. Oyala Junko Yano Elizaveta A. Suturina Muralee Murugesu Theodor Agapie 《Angewandte Chemie (International ed. in English)》2023,62(49):e202313880
Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*4W4Fe13S12 , displaying a Fe13 core with M−M bonds that has precedent only in main group and late metal chemistry. M13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*4W4Fe13S12 displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements. 相似文献
32.
Lukas Rochlitz Keith Searles Darryl F. Nater Scott R. Docherty Domenico Gioffrè Christophe Copéret 《Helvetica chimica acta》2021,104(7):e2100078
Propane dehydrogenation is an important field of research due to an increasing world-wide demand of propene while classical production routes through naphtha cracking are in decline. In that context, silica-supported Ga(III) sites, synthesized from surface organometallic chemistry principles, show high selectivity and stability in the propane dehydrogenation reaction. This performance is in significant contrast to the reported fast deactivation and lower selectivity of most Ga2O3 and CrO3 based materials. The Ga-catalyzed propane dehydrogenation reaction is proposed to proceed through the formation of Ga alkyl intermediates for which it would be desirable to have detailed structural and spectroscopic information. Here, we prepare a consistent series of Ga(III) molecular complexes with varying numbers of alkyl and siloxide ligands; they are characterized by single crystal X-Ray diffraction and X-Ray Absorption Near Edge Structure analysis, which is known to be highly sensitive to the Ga coordination environment. We report in particular the structure and the spectroscopic signatures of [Ga(iPr)(OSi(OtBu)3)2(HOSi(OtBu)3)], a molecular mimic of the key proposed reaction intermediates in the Ga-catalyzed PDH reaction. 相似文献
33.
Dr. Gabriele Hierlmeier Dr. Peter Coburger Dr. Daniel J. Scott Dr. Thomas M. Maier Dr. Stefan Pelties Prof. Dr. Robert Wolf Daniel M. Pividori Prof. Dr. Karsten Meyer Dr. Nicolaas P. van Leest Prof. Dr. Bas de Bruin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(60):14936-14946
Reactions of di-tert-butyldiphosphatetrahedrane ( 1 ) with cycloocta-1,5-diene- or anthracene-stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2-diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The subsequent reactivity of 1,2-diphosphacyclobutadiene cobaltates toward various electrophiles has also been investigated and is compared to reactions of related 1,3-diphosphacyclobutadiene complexes. The results highlight the distinct reactivity of such isomeric species, showing that the 1,2-isomers can act as precursors for previously unknown triphospholium ligands. The electronic structures of the new complexes were investigated by several methods, including NMR, EPR and Mößbauer spectroscopies as well as quantum chemical calculations. 相似文献
34.
Dr. Christian M. Hoidn Dr. Daniel J. Scott Prof. Dr. Robert Wolf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):1886-1902
Recently there has been great interest in the reactivity of transition-metal (TM) centers towards white phosphorus (P4). This has ultimately been motivated by a desire to find TM-mediated alternatives to the current industrial routes used to transform P4 into myriad useful P-containing products, which are typically indirect, wasteful, and highly hazardous. Such a TM-mediated process can be divided into two steps: activation of P4 to generate a polyphosphorus complex TM-Pn, and subsequent functionalization of this complex to release the desired phosphorus-containing product. The former step has by now become well established, allowing the isolation of many different TM-Pn products. In contrast, productive functionalization of these complexes has proven extremely challenging and has been achieved only in a relative handful of cases. In this review we provide a comprehensive summary of successful TM-Pn functionalization reactions, where TM-Pn must be accessible by reaction of a TM precursor with P4. We hope that this will provide a useful resource for continuing efforts that are working towards this highly challenging goal of modern synthetic chemistry. 相似文献
35.
36.
Dr. Ross McLellan Maria A. Palacios Dr. Christine M. Beavers Dr. Simon J. Teat Dr. Stergios Piligkos Prof. Euan K. Brechin Dr. Scott J. Dalgarno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2804-2812
Methylene‐bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis‐calix[4]arenes and transition metal ions or 3d‐4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures. 相似文献
37.
Facile Interchange of 3d and 4f Ions in Single‐Molecule Magnets: Stepwise Assembly of [Mn4], [Mn3Ln] and [Mn2Ln2] Cages within Calix[4]arene Scaffolds 下载免费PDF全文
Dr. Maria A. Palacios Dr. Ross McLellan Dr. Christine M. Beavers Dr. Simon J. Teat Dr. Høgni Weihe Dr. Stergios Piligkos Dr. Scott J. Dalgarno Prof. Euan K. Brechin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11212-11218
The central MnII ions in a series of calix[4]arene‐stabilised butterflies can be sequentially replaced with LnIII ions, maintaining the structural integrity of the molecule but transforming its magnetic properties. The replacement of MnII for GdIII allows for the examination of the transferability of spin‐Hamiltonian parameters within the family as well as permitting their reliable determination. The introduction of the 4f ions results in weaker intramolecular magnetic exchange, an increase in the number of low‐lying excited states, and an increase in magnetisation relaxation, highlighting the importance of exchange over single‐ion anisotropy for the observation of SMM behaviour in this family of complexes. The presence of the [TMII/III(TBC[4])(OH)(solvent)] metalloligand (TM=transition metal, TBC=p‐tBu‐calix[4]arene) suggests that magnetic calix[n]arene building blocks can be employed to encapsulate a range of different “guests” within structurally robust “hosts”. 相似文献
38.
Azidoethoxyphenylalanine as a Vibrational Reporter and Click Chemistry Partner in Proteins 下载免费PDF全文
Elise M. Tookmanian Prof. Dr. Christine M. Phillips‐Piro Prof. Dr. Edward E. Fenlon Prof. Dr. Scott H. Brewer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(52):19096-19103
An unnatural amino acid, 4‐(2‐azidoethoxy)‐L ‐phenylalanine (AePhe, 1 ), was designed and synthesized in three steps from known compounds in 54 % overall yield. The sensitivity of the IR absorption of the azide of AePhe was established by comparison of the frequency of the azide asymmetric stretch vibration in water and dimethyl sulfoxide. AePhe was successfully incorporated into superfolder green fluorescent protein (sfGFP) at the 133 and 149 sites by using the amber codon suppression method. The IR spectra of these sfGFP constructs indicated that the azide group at the 149 site was not fully solvated despite the location in sfGFP and the three‐atom linker between the azido group and the aromatic ring of AePhe. An X‐ray crystal structure of sfGFP‐149‐AePhe was solved at 1.45 Å resolution and provides an explanation for the IR data as the flexible linker adopts a conformation which partially buries the azide on the protein surface. Both sfGFP‐AePhe constructs efficiently undergo a bioorthogonal strain‐promoted click cycloaddition with a dibenzocyclooctyne derivative. 相似文献
39.
Frontispiece: Gd‐DTPA‐Dopamine‐Bisphytanyl Amphiphile: Synthesis,Characterisation and Relaxation Parameters of the Nanoassemblies and Their Potential as MRI Contrast Agents 下载免费PDF全文
40.
Dr. Catherine Adam Dr. Lixu Yang Dr. Scott L. Cockroft 《Angewandte Chemie (International ed. in English)》2015,54(4):1164-1167
Fluorocarbons often have distinct miscibility properties compared to their nonfluorinated analogues. These differences may be attributed to van der Waals dispersion forces or solvophobic effects, but their contributions are notoriously difficult to separate in molecular recognition processes. Here, molecular torsion balances were used to compare cohesive alkyl and perfluoroalkyl interactions in a range of solvents. A simple linear regression enabled the energetic partitioning of solvophobic and van der Waals forces in the self‐association of apolar chains. The contributions of dispersion interactions in apolar cohesion were found to be strongly attenuated in solution compared to the gas phase, but still play a major role in fluorous and organic solvents. In contrast, solvophobic effects were found to be dominant in driving the association of apolar chains in aqueous solution. The results are expected to assist the computational modelling of van der Waals forces in solution. 相似文献