Editor's Page Cite This: Organometallics XXXX, XXX, XXX−XXX
Expanding the Boundaries of Organometallic Chemistry
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s our community knows, Organometallics strives to capture the best chemistry relevant to our readership. Iconic molecules such as ferrocene, bis(benzene)chromium, and dimanganese dodecacarbonyl have long graced our pages, and research on these compounds continues to this day. Another classic molecule associated with organometallic chemistry and featured in many of our courses and papers published in Organometallics is Wilkinson’s catalyst, (Ph3P)3RhCl. This compound does not contain any metal−carbon bonds, yet does it and its chemistry belong in Organometallics? The answer is, of course, yes, and I think few would question its appropriateness for our readership. However, too often, our content is stereotyped as being limited to a narrow and strict class of compounds containing isolable and often crystallographically characterized metal−carbon bonds. As illustrated by the previous example, this is simply not true. The Editorial Team at Organometallics is actively trying to reverse this stereotype and hopes to attract great content from an author base that is as diverse as possible. To illustrate the scope and diversity of the papers we publish, we felt it timely to compile a Virtual Issue entitled “Expanding the Boundaries of Organometallic Chemistry,” comprised of papers that may seem outside the perceived scope of Organometallics. The virtual issue is available here. Our “Guidelines for Authors” is rather broad and is reproduced here to remind readers of the diverse chemistry we accept. “Furthermore, manuscripts dealing with metal-containing compounds that do not contain metal−carbon bonds will be considered if there is a close relationship between the subject matter and the principles and practice of organometallic chemistry. Such compounds may include, inter alia, representatives from the following classes: molecular metal hydrides; metal alkoxides, thiolates, amides, and phosphides; metal complexes containing organo-group 15 and 16 ligands; metal nitrosyls. Papers dealing with certain aspects of organophosphorus, organoselenium, and organosulfur chemistry also will be considered. In evaluating submissions that deal with subject matter that is peripheral to mainstream organometallic chemistry, the primary consideration is whether the manuscript is of interest to our readers.”
report titanate catalysts supported by nitrogen- and oxygenbased ligands and their use for the condensation cross-linking of siloxanes (DOI: 10.1021/acs.organomet.7b00335). Unlike the MOF example, metal−carbon bonds do not appear to be formed during the catalytic reaction. So why is this paper appropriate for Organometallics? The answer is that many of the concepts and principles in the Mejiá study are of interest to our readers. The manuscript reports the synthesis and structural characterization of the precatalysts along with detailed NMR spectroscopic studies of metal complexes likely formed during catalysis. The lessons learned from this work are no different from chemistry involving metal−carbon bond intermediates. Also in this vein of expanded interest, Paula Diaconescu (UCLA) and co-workers report detailed mechanistic studies on redox-switchable zirconium catalysts for the copolymerization of lactide and cyclohexene oxide (DOI: 10.1021/acs.organomet.7b00672). While a pendant ferrocene group is key for the redox behavior, the catalytic action is at the zirconium, which is ligated by nitrogen and oxygen ligands throughout the polymerization. Because the preferred pathway is coordination−insertion, comparisons to olefin polymerization are unavoidable. In chemistry more applicable to organic methods, Robert Flowers II (Lehigh University) and co-workers report the application of proton-coupled electron transfer to the reduction of ketones promoted by samarium iodide (DOI: 10.1021/acs.organomet.7b00392). While the metal plays a key role in promoting the overall transformation of the substrate, the data support radical intermediates. The detailed kinetic and thermodynamic studies in this manuscript make this work clearly within scope of Organometallics. Materials chemistry is also prominent in our Virtual Issue. A collaboration between founding Associate Editor Tobin Marks and Peter Stair (Northwestern University) and colleagues describes the chemisorption of a well-defined organometallic platinum pincer complex to prepare oxide-supported singleatom materials (DOI: 10.1021/acs.organomet.6b00869). Methods for reducing the speciation of the platinum are described, and vibrational spectroscopy was used to show that oxidized platinum species are inactive for the catalytic oxidation of CO. Sanjay Mathur (University of Cologne) and co-workers report a related study that used iridium cyclooctadiene complexes as precursors for the deposition of nanocrystalline films that can be converted to iridium dioxide (DOI: 10.1021/acs.organomet.7b00275). In this case, the metal−carbon bond opens the door to interesting materials chemistry. Unsurprising to readers of the journal, main-group compounds also exhibit a diverse chemistry relevant to our Virtual Issue. Alexander Spokoyny (UCLA) and co-workers published an article with the provocative title “Metal-Free Peralkylation of the closo-Hexaborate Anion” (DOI: 10.1021/ acs.organomet.7b00078). Some readers reacted with “What in
−Organometallics “Guidelines for Authors”
These contributions span the many fields where organometallic and related chemistry has a critical impact. The selection of these papers is by no means comprehensive, but rather illustrates the types of content we encourage. Not surprisingly, various forms of catalysis are represented. Mircea Dincă (MIT) and co-workers report the selective dimerization of propylene to branched hexenes by a nickel-containing metal organic framework (DOI: 10.1021/acs.organomet.7b00178). The MOF catalytic sites are analogous to more-familiar trispyrazolylborate nickel(II) complexes. While the MOF contains no observable metal−carbon bonds, the intermediates in the catalytic reactions undoubtedly do. In another paper, Esteban Mejiá (Leibniz Institute for Catalysis) and co-workers © XXXX American Chemical Society
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DOI: 10.1021/acs.organomet.8b00056 Organometallics XXXX, XXX, XXX−XXX
Organometallics
Editor's Page
the world is this paper doing in Organometallics?” Clearly metalfree belies the journal’s name! The answer is clear: Boron compounds, especially those with B−C bonds, have been of long-standing interest to our community. In addition to their structure and bonding, organoboron compounds exhibit exciting reactivity germane to our community. The Spokoyny paper also has many of the hallmarks readers enjoy in an Organometallics article, elegant synthetic work, beautiful molecular structures and insights into the redox properties and bonding in the molecules. In another example, Muriel Hissler (Université de Rennes 1), Jiři ́ Vohlidal (Charles University), and co-workers report metallosupramolecular polymers with phosphole central units that are assembled with metal ions, again highlighting the vibrancy of bonds between carbon and the main-group elements (DOI: 10.1021/acs.organomet.6b00822). Derek Gates (University of British Columbia) and co-workers, as part of the Special Issue “Tailoring the Optoelectronic Properties of Organometallic Compounds with Main-Group Elements” report the anionic polymerization of P-mesityl substituted phosphalkenes to produce brilliantly fluorescent polymers (DOI: 10.1021/acs.organomet.6b00880). Again, the molecules themselves may be outside the traditional purview of organometallic chemistry, but the story told is of interest to our readership combining materials chemistry, spectroscopy, and synthesis. We also selected examples from the field of bioorganometallic chemistry for the Virtual Issue. Konrad Kowalski (University of Łodz), Yu Chen (University of South Florida), and co-workers report the antibacterial properties of metallocenyl-7-aminode conjugates that depending on the identity of the transition metal have different levels of inhibition of a penicillin binding protein (DOI: 10.1021/acs.organomet.6b00888). It is not often protein crystal structures appear in the pages of Organometallics (We are enthusiastically awaiting more!), but this paper showcases the breadth of the field. As the authors state: “... protein crystals, even from biologically unrelated molecules, can be utilized to determine the structure of small molecules.” Clearly, a bright future lies ahead for this area of research. On another front, half-sandwich iridium compounds have often appeared in Organometallics, but their application to livecell imaging is also rare and a type of chemistry that many do not associate with the journal. Serge Thorimbert and Michèle Salmain (Sorbonne Universités, CNRS) and colleagues describe dyads based on this motif and evaluated the cytotoxicity of the metallodrug (DOI: 10.1021/acs.organomet.7b00250). We also published studies by Joseph Merola (Virginia Tech) and co-workers on the application of rhodium and iridium piano stool complexes as antimicrobial compounds (DOI: 10.1021/acs.organomet.7b00742). We are thrilled to receive these types of manuscripts and believe they strengthen both the field of organometallic chemistry and Organometallics, and we hope they will be an area of growth for the journal. So there you have it. Enjoy reading the sampling of articles we have highlighted in our latest Virtual Issue “Expanding the Boundaries of Organometallic Chemistry.” We hope this content reinforces the notion that organometallic chemistry is a vibrant field that has many brilliant facets and that Organometallics strives to be the journal of record that captures all of this great science. Through this effort, we hope to attract new authors to Organometallics, while at the same time
maintaining our standards for excellence that have been established by our current authorship. Paul Chirik Editor-in-Chief Organometallics
Paul J. Chirik
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Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States
AUTHOR INFORMATION
ORCID
Paul J. Chirik: 0000-0001-8473-2898 Notes
Views expressed in this editorial are those of the author and not necessarily the views of the ACS.
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DOI: 10.1021/acs.organomet.8b00056 Organometallics XXXX, XXX, XXX−XXX
