Comments on Inorganic Chemistry最新文献

{"title":"Ligand K-Edge XAS Studies of Metal-Phosphorus Bonds: Applications, Limitations, and Opportunities","authors":"Courtney M. Donahue, Scott R. Daly","doi":"10.1080/02603594.2018.1465938","DOIUrl":"https://doi.org/10.1080/02603594.2018.1465938","url":null,"abstract":"Phosphorus K-edge X-ray absorption spectroscopy (XAS) is a highly effective experimental method for investigating metal-phosphorus bonding and electronic structure. Here, we provide a comprehensive review of P K-edge XAS studies of transition metal complexes and show how they were used to investigate a wide range of chemical phenomena, including covalent metal-ligand bonding, redox non-innocence in ligands, molecular magnetism, and luminescence. Limitations of the technique are discussed along with opportunities for future work.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"11 1","pages":"54 - 78"},"PeriodicalIF":5.4,"publicationDate":"2018-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85278349","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Commentary on the Synthesis and Structures of Unsupported Cycloarsoxane Compounds","authors":"Mutasem Z. Bani-Fwaz, A. Fazary","doi":"10.1080/02603594.2018.1423618","DOIUrl":"https://doi.org/10.1080/02603594.2018.1423618","url":null,"abstract":"This comment describes the available synthetic routes and some general structural features of unsupported cycloarsoxane compounds. The key synthetic strategies used to prepare this type of compound and the significant roles that they have been employed in after coordination to the metal center are fully discussed. The literature herein covers all known unsupported cycloarsoxane compounds that have been structurally characterized by X-ray diffraction techniques.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"42 1","pages":"36 - 53"},"PeriodicalIF":5.4,"publicationDate":"2018-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76144402","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"All That Glitters Is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers—A Tribute to Al Cotton on the Tenth Anniversary of His Passing","authors":"Brooke M. Otten, Kortney M Melancon, M. Omary","doi":"10.1080/02603594.2018.1467315","DOIUrl":"https://doi.org/10.1080/02603594.2018.1467315","url":null,"abstract":"As the tenth year that follows the premature passing of the inorganic chemistry legend F. Albert (Al) Cotton comes to a close, we provide some soul food that we believe Al would have enjoyed as he looks down upon two generations of disciples, a grandchild and two great grandchildren, in his scientific family tree. This article also represents a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that nonetheless preserves the journal’s identity as a niche for “critical discussion of the current literature” of inorganic chemistry. Thus, we show novel demonstrations of a posteriori validation and a priori prediction of possible counterintuitive covalent M-M’ bonds—after and before synthesis, respectively—contrasted with non-covalent M···M interactions of the metallophilic type in bridge-dimeric systems of d10 metal centers. Mixing of (n + 1)s0/p0 orbitals with (n)d10 orbitals in the former heterobimetallics case—and lack thereof in the latter homobimetallics case—is hypothesized to be responsible for the presence or absence of covalency, respectively. However, we also demonstrate that the consequent d-s’ and/or d-p’ orbital mixing/hybridization can occur even in homobimetallic complexes that contain asymmetric bridging ligands (e.g., with -S^C- donor atoms that lead to orbital interactions between M-S and M-C fragments). Hence, the “control” metallophilic case for the hypothesized d10-d10 polar-covalent bonding herein is best manifest by M2(P^P)2 homobimetallics vis-à-vis M2(S^C)2 embodiments. Finally, we also offer a point/counterpoint commentary to the readers to contrast factors that argue for covalency vs metallophilicity and forewarn against exaggerating the extent of covalent bonding in such d10-d10 species. Thus, scrutinizing the various theoretical parameters has pointed to M-M’ and M-M partially bonded S^C-bridge dinuclear d10 complexes vis-à-vis the classic Cotton-type multiple metal-metal bond description in d0","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"49 1","pages":"1 - 35"},"PeriodicalIF":5.4,"publicationDate":"2018-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84365322","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"EOV Editoral Board","authors":"","doi":"10.1080/02603594.2017.1399689","DOIUrl":"https://doi.org/10.1080/02603594.2017.1399689","url":null,"abstract":"","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"7 6","pages":"327 - 327"},"PeriodicalIF":5.4,"publicationDate":"2017-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72635138","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Performance Vs Convenience of Magnetic Carbon-Metal Nanocomposites: A Low-Cost and Facile Citrate-Derived Strategy for Feco Alloy/Carbon Composites with High-Performance Microwave Absorption","authors":"Wenlei Chu, Chunhua Tian, Ying Wang, Jiayu Chu, Zhigang Li, Yunchen Du, Xijiang Han","doi":"10.1080/02603594.2017.1374257","DOIUrl":"https://doi.org/10.1080/02603594.2017.1374257","url":null,"abstract":"Magnetic carbon-based composites reside at the frontier of high-performance microwave absorbing materials (MAMs) due to their dual loss mechanisms and tunable electromagnetic properties. In this study, we review the construction of magnetic carbon-metal composites in recent years, and introduce a facile citrate-derived strategy to produce FeCo alloy/carbon composites through a direct pyrolysis of the resultant gels, where citric acid is employed as both a carbon source and a complexing agent. It is found that the dosage of citric acid determines the crystalline phase and particle size of magnetic FeCo alloy particles, as well as the content of carbon components. Electromagnetic analysis indicates that the electromagnetic functions of these composites are highly dependent on their specific compositions, where carbon components favor high complex permittivity and FeCo alloy particles take charge of complex permeability. When the chemical composition is optimized, good attenuation ability and characteristic impedance matching are created in the composite, resulting in desirable microwave absorption properties. The absorption performance is comparable to most homologous composites reported. Considering the low-cost and easy preparative process, we believe that this citrate-derived strategy may be instructive and helpful for practical applications of various magnetic carbon-based composites in the field of microwave absorption. Graphical Abstract","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"1 1","pages":"301 - 326"},"PeriodicalIF":5.4,"publicationDate":"2017-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73027619","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Methane Manifesto: A Theorist’s Perspective on Catalytic Light Alkane Functionalization","authors":"T. Cundari","doi":"10.1080/02603594.2016.1242487","DOIUrl":"https://doi.org/10.1080/02603594.2016.1242487","url":null,"abstract":"The catalytic functionalization of light alkanes, particularly methane, has attracted considerable attention from the inorganic and organic research communities for nearly five decades. The literature mechanisms for C—H activation may be divided into three broad categories: metal directed, ligand directed, or metal-ligand directed. The advantages for metal-ligand directed pathways have both steric and electronic origins. Furthermore, computations suggest that the stereoelectronic requirements for the activation and functionalization component reactions can be diametrically opposed. From this research, several questions emerge for theorists that would aid in the hunt for synthesizable complexes for efficient catalytic functionalization of light alkanes. First, is there a happy medium by which a complex is nucleophilic enough to activate a alkane C—H bond with a reasonable rate, but that is not so basic as to thwart the subsequent C—O,N bond-forming step? Second, what are the energetic consequences of moving along the “ide”/“yl” continuum? Third, how can the electronic coupling among the three main catalyst components—metal, actor ligand, and spectator ligand—be modulated to permit the use of Earth-abundant catalysts to effect catalytic functionalization of light alkanes?","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"113 1","pages":"219 - 237"},"PeriodicalIF":5.4,"publicationDate":"2017-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79395515","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic Aspects of Copper-Catalyzed Decarboxylative Coupling Reactions of (Hetero)Aryl Carboxylic Acids","authors":"J. Hoover","doi":"10.1080/02603594.2016.1261023","DOIUrl":"https://doi.org/10.1080/02603594.2016.1261023","url":null,"abstract":"Copper-catalyzed oxidative decarboxylative coupling reactions of benzoic acids have emerged as attractive routes to access functionalized arenes. Unfortunately, substrate scope limitations and forcing reaction conditions have prevented the widespread implementation of these methodologies. A mechanistic understanding of these systems could enable the development of more robust reactions, yet few studies have targeted the mechanistic elucidation of these complex systems. This article reviews the copper-catalyzed decarboxylation reactions of hetero(aromatic) acids, including protodecarboxylations, redox-neutral decarboxylative couplings, and oxidative decarboxylative coupling reactions. We emphasize the mechanistic insights learned from each system to build a framework for understanding copper-catalyzed decarboxylative coupling reactions.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"96 1","pages":"169 - 200"},"PeriodicalIF":5.4,"publicationDate":"2017-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88307219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Holmium for Use in Cancer Therapy","authors":"Yi Shi, A. Johnsen, A. D. Di Pasqua","doi":"10.1080/02603594.2017.1333498","DOIUrl":"https://doi.org/10.1080/02603594.2017.1333498","url":null,"abstract":"Over the last few decades, holmium (Ho) has been investigated for its application in laser surgery, magnetic resonance imaging, and internal and topical radionuclide therapy. Ho has a 100% natural abundance of holmium-165, which is a stable nuclide that can undergo a process called neutron-activation to generate radioactive holmium-166 (166Ho). 166Ho emits β–particles and γ photons, with a half-life of 26.8 h; β–particles can damage a cancer cell’s DNA, while γ photons allow for 166Ho to be imaged in vivo and easily quantitated prior to, or during, dosing. This article gives a thorough account of the work being done around the world on 166Ho for use as an internal or topical radionuclide therapy against cancer. Our research group and others have generated compelling data that support the use of 166Ho as a radiotherapeutic in the clinic, especially since pharmaceutical formulations can be made while non-radioactive (Ho) and then made radioactive (166Ho) just prior to use. Graphical Abstract","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"65 1","pages":"281 - 300"},"PeriodicalIF":5.4,"publicationDate":"2017-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89322137","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Strategies for Tuning Emission Energy in Phosphorescent Ir(III) Complexes","authors":"A. Huckaba, M. Nazeeruddin","doi":"10.1080/02603594.2016.1207064","DOIUrl":"https://doi.org/10.1080/02603594.2016.1207064","url":null,"abstract":"Graphical Abstract Research into phosphorescent Ir(III) complexes has grown immensely since their first report. Talented chemists have successfully synthesized complexes capable of emitting from the ultraviolet to the near-infrared regions of the electromagnetic spectrum. Tuning the emission energy in a selective manner requires knowledge of how ligand substitution affects not only energy levels such as the highest occupied molecular orbital and lowest unoccupied molecular orbital, but also the emissive triplet energy level. This review describes fundamental principles involved in energy-level engineering and substituent selection as well as fundamental methods of device characterization.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"110 1","pages":"117 - 145"},"PeriodicalIF":5.4,"publicationDate":"2017-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79247539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hybrid Antioxidant and Metal Sequestering Small Molecules Targeting the Molecular Features of Alzheimer’s Disease","authors":"K. Green, Hannah M. Johnston, Marianne E. Burnett, Samantha M. Brewer","doi":"10.1080/02603594.2016.1241616","DOIUrl":"https://doi.org/10.1080/02603594.2016.1241616","url":null,"abstract":"Graphical Abstract Alzheimer’s disease currently affects over 5.4 million Americans with $236 billion spent annually on the direct costs of patient care. Health experts expect this price tag to rise to $1.1 trillion by 2050 if intervention for disease progression is not found. Alzheimer’s disease is the sixth leading cause of death in the U.S. and the only disease in the top 10 causes of death that cannot currently be prevented or slowed. Of these deaths, two-thirds of Alzheimer’s disease victims are women. These statistics reflect an immediate worldwide need to understand the series of mechanisms that give rise to Alzheimer’s disease. With this understanding, we can develop therapeutic interventions for the disease. Here, we will discuss a selection of small molecules that have been recently developed to target the known molecular features of Alzheimer’s disease: amyloid-beta protein and oxidative stress. These potential therapeutics include small molecules inspired by early therapeutic potential demonstrated by the molecule clioquinol as well as divergent work that combines other metal-binding and antioxidant building blocks into one scaffold. The results related to the molecular features of Alzheimer’s disease will be presented.","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"37 1","pages":"146 - 167"},"PeriodicalIF":5.4,"publicationDate":"2017-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76723905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}