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Undergraduate Research: Contributions to Organometallic Chemistry
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events. For example, CUR’s Posters on the Hill held in Washington, DC, is a competitive event that gives students the opportunity to showcase their research to congressional members, meet with their representatives, and learn about advocacy for undergraduate research.3 At the institutional level, PUIs are increasingly establishing undergraduate research centers to address support issues. Bowling Green State University’s Center for Undergraduate Research & Scholarship is just one example.4 Individual chemistry departments and faculty continue to leverage resources in creative ways, through collaborations with faculty at research universities to expand equipment access and by developing multiple-PUI consortia to leverage acquisition of shared instrumentation. Undergraduate research experiences also continue to evolve through introduction of more course-based research projects in a variety of chemical disciplines.5−7 The PUI researchers featured in this Virtual Issue represent a broad spectrum of institutions across the U.S. and Canada, career levels of faculty, and areas of interest, but they all share the common purpose of the pursuit of high-quality research with undergraduates. The success of this goal is demonstrated both by the quality of the research and the range of funding agencies that supported the work. These sources include both private foundations (ACS Petroleum Research Fund, Camille & Henry Dreyfus Foundation, Research Corporation, and the Robert A. Welch Foundation) and federal agencies (NIH, NSERC, and NSF). This range and level of support rivals that of principal investigators at major research universities. The articles we have highlighted (see Table 1) were selected from four core journals publishing organometallic chemistry research and appeared from 2014 to 2018: Organometallics, Inorganic Chemistry, Organic Letters, and The Journal of Organic Chemistry. These reports span the gamut of approaches to organometallic chemistry, ranging from solely computational work to stoichiometric synthetic studies and metal-catalyzed transformations. Topical areas of focus are also incredibly diverse, tapping into coordination chemistry, electrocatalysis/ electrochemistry, main-group studies, materials science, and small-molecule activation. Timely research themes include C−H borylation, CO2 reduction, and earth-abundant-metal catalysis, to name just a few. It is clear from these highlighted reports that PUI researchers strive to maintain a presence in emerging frontier areas of organometallic research. We encourage you to share the table with colleagues and students and to consider using these papers to spur literature discussions in your inorganic courses to show undergraduates how they can have a direct impact in the field of organometallics.8
esearch carried out at Primarily Undergraduate Institutions (PUIs) is a distinctive feature of colleges and universities in North America. The origin of these PUIs’ contributions to the advancement of science, technology, engineering, and mathematics dates to the significant number of small private liberal arts colleges that were established during the growth of the American higher education system in the 19th century which still exists today. Today the term PUI has a broader context, being defined by the U.S. National Science Foundation: PUIs are “two-year, four-year, and masters-level programs... but may have awarded 20 or fewer Ph.D./D.Sci. degrees in all NSF-supported fields during the previous two academic years”.1 Although the work of graduate student researchers is considered, the major contributions to research publications from PUIs typically come from undergraduates. To honor those contributions, we are proud to present a Virtual Issue (https://pubs.acs.org/page/orgnd7/vi/organometallicundergradresearch.html) with organometallic chemistry contributions from 24 PUI research groups in the U.S. and Canada. PUIs in many ways offer a stark contrast to the research environments found at Ph.D.-granting institutions. In most doctorate programs, students receive significant hands-on training from senior graduate students or postdoctoral associates, and they rely on faculty to assist in experiment and project design. By contrast, professors directing undergraduates at PUIs serve the dual responsibility of training students in experimental techniques or methods while mentoring students in their development toward becoming independent scientists. As a result of the intensive nature of this expanded role, small research groups are the norm at PUIs. For the student, providing expanded access to Ph.D.-level scientists in both the classroom and laboratory settings is a tremendous opportunity during a critical juncture in their education, when decisions on career tracks and the pursuit of advanced degrees are made. The value of the PUI research experience is unquestionable, as PUIs consistently send higher percentages of students to graduate programs relative to that from larger, primarily research-focused institutions.2 As we can attest, PUI faculty face significant and unique challenges. Higher teaching loads, e.g., three or four class or lab sections per semester, are often the expectation, creating demands on time. PUI faculty also face inconsistent levels of administration and research support, resulting in a multitude of barriers, including lack of suitable startup funds, less than optimal research space, inadequate access to instrumentation, minimal grant support, and the absence of extensive library resources. Despite these constraints, there has never been a greater commitment from PUIs and their faculty, in particular in chemistry, to deliver authentic research experiences to students. National organizations, such as The Council on Undergraduate Research (CUR), provide guidance in developing healthy research environments at PUIs while also affording opportunities for students to present their findings at national © XXXX American Chemical Society
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CONCLUSION The research featured in this Virtual Issue is a testament to the high-level work that can be performed with undergraduates.
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DOI: 10.1021/acs.organomet.8b00369 Organometallics XXXX, XXX, XXX−XXX
Organometallics
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Table 1. Organometallic Research at Primarily Undergraduate Institutions Highlighted in this Virtual Issue college/university
journal
paper title
synopsis
Ariana L. Tribby, Ismerai ́ ́ Rodriguez, Shamira, Shariffudin, and Nicholas D. Balla
researchers
Pomona Collegeb and Amherst College
The Journal of Organic Chemistry
A versatile palladium-catalyzed route to aryl sulfonyl fluorides was developed.
BriAnne Bentivegna, Christine I. Marian, Jason R. Smith, Shuhua Ma, Arnold L. Rheingold, and Tim J. Brunkera
Towson University
Organometallics
Daniel Kim, Linh Le, Myles J. Drance, Kelsey H. Jensen, Kristijan Bogdanovski, Tia N. Cervarich, Melissa G. Barnard, Natalie J. Pudalov, Spring Melody M. Knapp, and Anthony R. Chianesea Heather R. Wiltse, Alyssa N. Johnson, Raphael J. Durand, William Brennessel, and Robert M. China
Colgate University
Organometallics
Pd-Catalyzed Conversion of Aryl Iodides to Sulfonyl Fluorides Using SO2 Surrogate DABSO and Selectfluor (DOI: 10.1021/acs.joc. 7b00051) Formation, Stability, and Structures of Borenium and Boronium Cations Derived from Pentamethylazaferrocene−Boranes by Hydride or Chloride Abstraction Reactions (DOI: 10.1021/ om500348u) Ester Hydrogenation Catalyzed by CNN-Pincer Complexes of Ruthenium (DOI: 10.1021/acs. organomet.6b00009)
University of Northern Iowa
Organometallics
Syntheses, Characterization, and Reactivity of Diruthenium Hydrido Complexes (DOI: 10.1021/acs. organomet.6b00067)
Lillian V. A. Hale, Kathryn A. McGarry, Marissa A. Ringgold, and Timothy B. Clarka
University of San Diego
Organometallics
Role of Hemilabile Diamine Ligands in the Amine-Directed C−H Borylation of Arenes (DOI: 10. 1021/om5007837)
Paul J. Fischer,a Laura Avena, Trent D. Bohrmann, Michelle C. Neary, Grace K. Putka, and Kevin P. Sullivan
Macalester College
Organometallics
Timothy W. Funk,a Andrew R. Mahoney, Rebecca A. Sponenberg, Kathryn P. Zimmerman, Daniel K. Kim, and Emily E. Harrison
Gettysburg College
Organometallics
Mayra Delgado, Joshua M. Zieglar, Takele Seda, Lev N. Zakharov, and John D. Gilbertsona
Western Washington University
Inorganic Chemistry
Kyle A. Gricea and Cesar Saucedo
DePaul University
Inorganic Chemistry
Group VI Metal Carbonyl Complexes of Bis ((diphenylphosphino)methyl) diphenylborate and an Assessment of Their Utility for Template Ligand Syntheses (DOI: 10.1021/ om5001056) Synthesis and Catalytic Activity of (3,4-Diphenylcyclopentadienone) Iron Tricarbonyl Compounds in Transfer Hydrogenations and Dehydrogenations (DOI: 10.1021/ acs.organomet.8b00037) Pyridinediimine Iron Complexes with Pendant Redox-Inactive Metals Located in the Secondary Coordination Sphere (DOI: 10. 1021/acs.inorgchem.5b02544) Electrocatalytic Reduction of CO2 by Group 6 M(CO)6 Species without “Non-Innocent” Ligands (DOI: 10.1021/acs.inorgchem. 6b00875) Mechanistic Studies on Platinum(II) Catalyzed Hydroarylation of Alkynes (DOI: 10.1021/om5003123)
Texas A&M Christine Hahn,a Mayra Miranda, Nagendra P. B. Chittineni, Trent A. University-Kingsvilleb Pinion, and Ricardo Perez and University of Texas of the Permian Basin Jeffrey Carroll, Hannah G. Woolard, East Carolina Robert Mroz, Charles A. Nason, University and Shouquan Houa
Organometallics
Joseph M. Dennis, Chad T. Compagner, Stanna K. Dorn, and Jeffrey B. Johnsona
Hope College
Organic Letters
Logan W. Sardzinski, William C. Wertjes, Abigail M. Schnaith, and Dipannita Kalyania
St. Olaf College
Organic Letters
James G. Koch, William W. Brennessel, and Bradley M. Krafta
St. John Fisher College
Organometallics
Alex D. Hunter, Trevor Robert Williams, Brandon M. Zarzyczny, Hans W. Bottesch II, Sara A. Dolan,
Lycoming College
Organometallics
Organometallics
Regiospecific Acylation of Cycloplatinated Complexes: Scope, Limitations, and Mechanistic Implications (DOI: 10.1021/acs. organomet.6b00174) Rhodium-Catalyzed Interconversion of Quinolinyl Ketones with Boronic Acids via C−C Bond Activation (DOI: 10.1021/acs.orglett.6b01434) Nickel-Catalyzed Decarboxylative Cross-Coupling of Perfluorobenzoates with Aryl Halides and Sulfonates (DOI: 10. 1021/acs.orglett.5b00241) Neutral and Cationic Bis-Chelate Monoorganosilicon(IV) Complexes of 1-Hydroxy-2-pyridinone (DOI: 10.1021/acs.organomet.6b00796) Correlations among 31P NMR Coordination Chemical Shifts, Ru−P Bond Distances, and B
Borenium cations were prepared through abstraction reactions from azaferrocene borane complexes and characterized by spectroscopic, crystallographic, and computational studies. Pyridyl NHC amine ruthenium pincer complexes were explored as ester hydrogenation catalysts.
Doubly linked dicyclopentadienide (Cp) ligands were used as supports for cationic diruthenium hydrido complexes that mediate catalytic C−H bond silylation of arenes. A comprehensive study of diamine ligand role in the iridium catalyzed ortho borylation of aromatic substrates containing heteroatom directing groups was performed. Spectroscopic and crystallographic investigation of the coordination chemistry of bis(phosphino)borates with molybdenum(0) was pursued.
A series of cyclopentadienone iron tricarbonyl complexes were prepared and assayed in catalytic transfer hydrogenation/dehydrogenation of carbonyl compounds and alcohols. Synthesis of pyridine diimine (PDI) iron complexes incorporating crown ether moieties and studies of electronic perturbations at iron upon ion encapsulation were explored. Comparative investigation of groups 6 and 7 metal carbonyls in the electrochemical reduction of CO2 to CO was performed. Stoichiometric, low temperature reactivity of a cationic platinum(II) acetylene complex and various arenes was studied, with implications for alkyne hydroarylation. Stoichiometric investigations of the role of hydrogen bonding in directing regioselective acylation in cyclometalated platinum complexes were conducted. An efficient rhodium-mediated crosscoupling was developed, providing a general protocol for C−C bond formation that overcomes substrate limitations in related systems. A versatile base-metal-catalyzed decarboxylative cross-coupling of electron poor benzoates with aryl halides and pseudohalides was described. The solution and solid-state structures of neutral and cationic organosilicon compounds bearing 1-oxo-2-pyridinone (OPO) ligands were investigated. Relationships between a range of properties, including Tolman cone angle,
DOI: 10.1021/acs.organomet.8b00369 Organometallics XXXX, XXX, XXX−XXX
Organometallics
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Table 1. continued researchers
college/university
journal
paper title
Kimberly A. McDowell, Dominique Nicole Thomas, and Charles H. Mahlera Brittany L. Blass, Raúl Hernández Sánchez, Victoria A. Decker, Michael J. Robinson, Nicholas A. Piro, W. Scott Kassel, Paula L. Diaconescu, and Chip Nataroa
Lafayette College
Organometallics
Andrew Ruff, Christopher Kirby, Benny C. Chan, and Abby R. O’Connora
The College of New Jersey
Organometallics
Kate E. McPherson, Libero J. Bartolotti, Andrew T. Morehead Jr., and Andrew L. Sargenta
East Carolina University
Organometallics
Jeremy M. Hines, Jesse J. Eason, and Matthew R. Sieberta
Missouri State University
Organometallics
Taylor Vacala, Lauren P. Bejcek, Chloé G. Williams, Alexandra C. Williamson, and Paul A. Vadolaa
DePaul University
The Journal of Organic Chemistry
Michael D. Turlington, Jared A. Pienkos, Elizabeth S. Carlton, Karlee N. Wroblewski, Alexis R. Myers, Carl O. Trindle, Zikri Altun, Jeffrey J. Rack, and Paul S. Wagenknechta Andrew J. Schwartz, Robert D. Pike, Rolfe H. Herber, and Eric J. Watsona
Furman University
Inorganic Chemistry
Seattle University
Organometallics
Marc G. Civit, Xavier Sanz, Christopher M. Vogel, Jonathan D. Webb, Stephen J. Geier, Andreas Decken, Carles Bo, Stephen A. Westcott,a and Elena Fernández Matthew T. Whited,a,b Lisa Qiu, Alex J. Kosanovich, and Daron E. Janzen
Mount Allison University
The Journal of Organic Chemistry
Carleton Collegeb and St. Catherine University
Inorganic Chemistry
a
PUI principal investigator. bPrimary intellectual driver of the publication.
Despite the many challenges that exist at PUIs, timely projects structured around emerging areas within organometallic chemistry are pursued at colleges and universities across North America. Research for undergraduates is often a transformative experience, providing a natural incubator for the next generation of organometallic chemists. We are delighted to highlight recent impactful reports from PUI researchers in the field, and we are optimistic that valuable contributions from PUIs will continue to increase in the coming years.
synopsis
Enthalpies of Reaction in Cp′Ru (PR3)2Cl Complexes (DOI: 10. 1021/acs.organomet.6b00444)
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Structural, Computational, and Spectroscopic Investigation of [Pd (κ3-1,1′-bis(di-tert-butylphosphino) ferrocenediyl)X]+ (X = Cl, Br, I) Compounds (DOI: 10.1021/acs. organomet.5b00889) Base-Free Transfer Hydrogenation of Ketones Using CpaIr (pyridinesulfonamide)Cl Precatalysts (DOI: 10.1021/acs. organomet.5b00864) Utility of the Nudged Elastic Band Method in Identifying the Minimum Energy Path of an Elementary Organometallic Reaction Step (DOI: 10.1021/acs.organomet. 6b00236) One Lump or Two? A Plurality of Pathways in Gold(III)-Catalyzed Cyclization Transforming Propargyl Acetates to a Carene-like Bicyclo [4.1.0]heptane (DOI: 10.1021/acs. organomet.6b00946) Gold-Catalyzed Hydroarylation of N-Aryl Alkynamides for the Synthesis of 2-Quinolinones (DOI: 10.1021/acs.joc.6b02984) Complexes with Tunable Intramolecular Ferrocene to TiIV Electronic Transitions: Models for Solid State FeII to TiIV Charge Transfer (DOI: 10.1021/acs. inorgchem.5b02587) Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene (DOI: 10.1021/acs.organomet. 5b00913) Thioboration of α,β-Unsaturated Ketones and Aldehydes toward the Synthesis of β-Sulfido Carbonyl Compounds (DOI: 10.1021/ jo5026354) Chalcogen Extrusion from Heteroallenes and Carbon Monoxide by a Three-Coordinate Rh(I) Disilylamide (DOI: 10.1021/ acs.inorgchem.5b00305)
Studies of Pd−Fe interactions in 1,1′-bis(di-tert-butylphosphino) ferrocene (dtpf) complexes of palladium and their implications for reactivity were explored.
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P NMR shift, and average crystallographic Ru−P bond distance, in ruthenium complexes were established.
Chelating pyridine sulfonamide ligands were assayed as flexible supports in airand moisture-tolerant iridium complexes, for use in transfer hydrogenation catalysis. A reexamination of intermediate energetics in hydroacylation, with particular emphasis on the oxidative addition step, using the NEB method was conducted. A quantum chemical computational study of potential mechanisms operative in the Ohloff-Rautenstrauch rearrangement was performed. A mild, modular gold-mediated access of 2-quinolines was developed, via hydroarylation of N-aryl alkynamides. Synthesis and investigation of MMCT behavior of a series of titanocene bis (alkynyl) complexes was explored.
Preparation and characterization of new homo- and heterometallic triple-decker sandwiches was accomplished, with potential applications in molecular electronics. Thioborane reagents promoted additivefree synthesis of β-sulfido ketones and aldehydes in moderate to excellent yields in a simple, one-pot reaction. Reactivity of a Rh(I) disilylamide was explored with a range of heteroallenes (CS2, OCS, and isocyanates) and CO, with potential application to heteroatom group transfer catalysis.
AUTHOR INFORMATION
Corresponding Authors
*E-mail:
[email protected]. *E-mail:
[email protected]. Present Address #
C.A.B.: U.S. Department of Energy, Basic Energy Sciences, 19901 Germantown Road, Germantown, MD 20874, United States. Notes
Views expressed in this editorial are those of the authors and not necessarily the views of the ACS.
Christopher A. Bradley*,†,# Chip Nataro*,‡
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DEDICATION We dedicate this virtual issue to the diligent and committed faculty at PUIs everywhere for providing mentorship to the next generation of organometallic chemists. We also thank our
Department of Science, Mount St. Mary’s University, Emmitsburg, Maryland 21727, United States ‡ Department of Chemistry, Lafayette College, Easton, Pennsylvania 18042, United States C
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current and former students, whose curiosity and enthusiasm for chemistry continue to motivate and inspire us.
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REFERENCES
(1) Facilitating Research at Primarily Undergraduate Institutions. https://www.nsf.gov/funding/pgm_summ.jsp?pims_id=5518 (accessed on 5-30-18). (2) The Colleges Where PhD’s Get Their Start. http://www. thecollegesolution.com/the-colleges-where-phds-get-their-start (accessed on 5-30-18). (3) 2018 Posters on the Hill. Council on Undergraduate Research.http://www.cur.org/conferences_and_events/student_ events/posters_on_the_hill (accessed on 5-30-18). (4) Bowling Green State University Undergraduate Research & Scholarship. http://www.bgsu.edu/provost/center-for-undergraduateresearch-and-scholarship (accessed on 5-30-18). (5) Dillner, D. K.; Ferrante, R. F.; Fitzgerald, J. P.; Schroeder, M. J. J. Chem. Educ. 2011, 88, 1623−1629. (6) Canaria, J. A.; Schoffstall, A. M.; Weiss, D. J.; Henry, R. M.; Braun-Sand, S. B. J. Chem. Educ. 2012, 89, 1371−1377. (7) Clark, T. M.; Ricciardo, R.; Weaver, T. J. Chem. Educ. 2016, 93, 56−63. (8) Duncan, A. P.; Johnson, A. R.; Nataro, C. Organometallics 2017, 36, 2703−2705.
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