Jaqueline Kiplinger

Last updated
Jaqueline Kiplinger
Jaqueline L. Kiplinger profile-photo.jpg
Nationality American
Alma mater University of Colorado
University of Utah
Scientific career
Institutions Los Alamos National Laboratory
Thesis Activation and Functionalization of Carbon-Fluorine Bonds by Transition Metal Complexes  (1996)

Jaqueline Kiplinger is an American inorganic chemist who specializes in organometallic actinide chemistry. Over the course of her career, she has done extensive work with fluorocarbons and actinides. She is currently a Fellow of the Materials Synthesis and Integrated Devices group in the Materials Physics and Applications Division of Los Alamos National Laboratory (LANL). [1] Her current research interests are focused on the development of chemistry for the United States’ national defense and energy needs.

Contents

Education

Kiplinger received her B.S. degree in chemistry from the University of Colorado at Colorado Springs in 1990. Under the guidance of Professor Ruminiski, Kiplinger has published several papers reporting coordination chemistry of iron and ruthenium featuring multidentate pyrazine-based ligands. [2] [3]

Kiplinger did her graduate studies at the University of Utah working with Professor Thomas Richmond. Her work focused on using organometallic species to break carbon-fluorine bonds in perfluoroalkanes, which are usually unreactive due to fluorine’s high electronegativity and the strength of the carbon-fluorine bond. [4] One notable publication in Organometallics displayed a novel transformation of an aromatic carbon-fluorine bond to a carbon-carbon bond using tungsten(II), shown below. [5] Additionally, Kiplinger and Richmond reported zirconium complexes that catalyze aromatic fluorocarbon hydrogenolysis. [6]

From 1996 to 1999, Kiplinger worked as a postdoctoral researcher at UC Berkeley under Professor Robert G. Bergman.

Career

Following her postdoctoral work, Kiplinger was awarded the Frederick Reines Distinguished Postdoctoral Fellowship at LANL. There, she started the program focused on the chemistry of actinides and lanthanides in the group led by Dr. Carol Burns. In 2002, Kiplinger, Burns, and co-workers published the first f-block elemental complex containing a ketimido group. [7] This was the first of many papers the group published pertaining to organometallic uranium chemistry. Soon after, Kiplinger and coworkers reported the first actinide hydrazonato complex using U(IV). [8] During that time, Kiplinger also reported improved synthesis of uranium-based metallocene complexes (C5Me5)U(CH2C6H5)3. [9]

Kiplinger continued her research at LANL after the conclusion of her fellowship, and she serves as a laboratory Fellow in the chemistry division to this day. She continued developing lanthanide and actinide chemistry, and published the synthesis of the first uranium and thorium halide complexes with tert-butyl substituted ketiminate ligands in 2013. [10]

In 2016, Kiplinger reported the synthesis of an infinite thorium diazide coordination polymer; the first such polymer involving an actinide. [11] The infinite property is unique to thorium azide complexes compared to other actinide metallocenes, such as uranium, which polymerize into trimers. By making alterations on the classic cyclopentadiene groups, different coordination polymers can be formed. [11] (C5Me5)2Th(N3)2 utilizes pentamethylcyclopentadiene to form polymers with two bridging azide groups, while (C5Me4Et)2Th(μ-η11-N3)(N3) uses ethyl-tetramethylcyclopentadiene caps to create a polymer with one bridging azide and one terminal azide group. [11] Her recent efforts have been focused on the chemistry of uranium and thorium compounds with nitrogen-rich ligands. [12] For example, experimental and theoretical work from her group revealed that tetrazolate ligands of these complexes act as sigma donors. [13]

Kiplinger Synthesis.jpg

Thorium Metallocene Borohydride Thorium Metallocene Borohydride.png
Thorium Metallocene Borohydride

Another important thrust in her research involved the development of redox chemistry with uranium hydrides. [12] She showed that phenylsilane can be used as a convenient stoichiometric reagent producing well-defined uranium (III), uranium (IV), and uranium (VI) complexes. [14] [12] Her more recent work details a new route to uranium and thorium metallocene borohydrides. The uranium complex had been synthesized previously from tetravalent uranium pentamethylborohydride and potassium cyclopentadiene, but the new synthesis using calcium borohydride and pentamethylcyclopentadienyl uranium chloride resulted in a higher yield under milder conditions. [15] While the preparation of U(BH4)4 is dated to the seminal work of Schlesinger and Brown in 1940s, this is the first example of a thorium metallocene borohydride. [15]

Awards

2018 Fellow of the American Chemical Society [16]

2017 IUPAC International Distinguished Women in Chemistry Award [17]

2016 University of Utah Distinguished Chemistry Alumna Award [18]

2015 ACS F. Albert Cotton Award in Synthetic Inorganic Chemistry [19]

2013-2014 Organometallic Subdivision Chair, ACS Division of Inorganic Chemistry [20]

2012 R&D 100 Award for U-TURN: Turning Uranium Around Process [21]

2012- Fellow of the Royal Society of Chemistry

2012- National Nuclear Security Administration Environmental Stewardship Award

2010- National Nuclear Security Administration Best-in-Class Pollution Prevention Award

1998 ACS Nobel Laureate Signature Award for the best Ph.D. thesis in the U.S. [22]

Related Research Articles

<span class="mw-page-title-main">Metallocene</span>

A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5
H
5
, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride, vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.

<span class="mw-page-title-main">Cyclopentadienyl complex</span> Coordination complex of a metal and Cp⁻ ions

A cyclopentadienyl complex is a coordination complex of a metal and cyclopentadienyl groups. Cyclopentadienyl ligands almost invariably bind to metals as a pentahapto (η5-) bonding mode. The metal–cyclopentadienyl interaction is typically drawn as a single line from the metal center to the center of the Cp ring.

<span class="mw-page-title-main">Organoactinide chemistry</span> Study of chemical compounds containing actinide-carbon bonds

Organoactinide chemistry is the science exploring the properties, structure and reactivity of organoactinide compounds, which are organometallic compounds containing a carbon to actinide chemical bond.

<span class="mw-page-title-main">Germylene</span> Class of germanium (II) compounds

Germylenes are a class of germanium(II) compounds with the general formula :GeR2. They are heavier carbene analogs. However, unlike carbenes, whose ground state can be either singlet or triplet depending on the substituents, germylenes have exclusively a singlet ground state. Unprotected carbene analogs, including germylenes, has a dimerization nature. Free germylenes can be isolated under the stabilization of steric hindrance or electron donation. The synthesis of first stable free dialkyl germylene was reported by Jutzi, et al in 1991.

Gregory S. Girolami is the William H. and Janet G. Lycan Professor of Chemistry at the University of Illinois at Urbana-Champaign. His research focuses on the synthesis, properties, and reactivity of new inorganic, organometallic, and solid state species. Girolami has been elected a fellow of the American Association for the Advancement of Science, the Royal Society of Chemistry, and the American Chemical Society.

<span class="mw-page-title-main">Actinocene</span>

Actinocenes are a family of organoactinide compounds consisting of metallocenes containing elements from the actinide series. They typically have a sandwich structure with two dianionic cyclooctatetraenyl ligands (COT2-, which is C
8
H2−
8
) bound to an actinide-metal center (An) in the oxidation state IV, resulting in the general formula An(C8H8)2.

Russell P. Hughes an American/British chemist, is the Frank R. Mori Professor Emeritus and Research Professor in the Department of Chemistry at Dartmouth College. His research interests are in organometallic chemistry, with emphasis on the chemistry of transition metal complexes interacting with fluorocarbons. His research group’s work in this area led to several creative syntheses of complexes of transition metal and perfluorinated hydrocarbon fragments.

Parisa Mehrkhodavandi is a Canadian chemist and Professor of Chemistry at the University of British Columbia (UBC). Her research focuses on the design of new catalysts that can effect polymerization of sustainably sourced or biodegradable polymers.

<span class="mw-page-title-main">Decamethylsilicocene</span>

Decamethylsilicocene, (C5Me5)2Si, is a group 14 sandwich compound. It is an example of a main-group cyclopentadienyl complex; these molecules are related to metallocenes but contain p-block elements as the central atom. It is a colorless, air sensitive solid that sublimes under vacuum.

<span class="mw-page-title-main">Zirconocene</span> Chemical compound

Zirconocene is a hypothetical compound with 14 valence electrons, which has not been observed or isolated. It is an organometallic compound consisting of two cyclopentadienyl rings bound on a central zirconium atom. A crucial question in research is what kind of ligands can be used to stabilize the Cp2ZrII metallocene fragment to make it available for further reactions in organic synthesis.

<span class="mw-page-title-main">(Pentamethylcyclopentadienyl)aluminium(I)</span> Chemical compound

(Pentamethylcyclopentadienyl)aluminium(I) is an organometallic compound with the formula Al(C5Me5) ("Me" is a methyl group; CH3). The compound is often abbreviated to AlCp* or Cp*Al, where Cp* is the pentamethylcyclopentadienide anion (C5Me5). Discovered in 1991 by Dhmeier et al., AlCp* serves as the first ever documented example of a room temperature stable monovalent aluminium compound. In its isolated form, Cp*Al exists as the tetramer [Cp*Al]4, and is a yellow crystal that decomposes at temperatures above 100 °C but also sublimes at temperatures above 140 °C.

<span class="mw-page-title-main">Plumbylene</span>

Plumbylenes (or plumbylidenes) are divalent organolead(II) analogues of carbenes, with the general chemical formula, R2Pb, where R denotes a substituent. Plumbylenes possess 6 electrons in their valence shell, and are considered open shell species.

<span class="mw-page-title-main">Lanthanocene</span>

A lanthanocene is a type of metallocene compound that contains an element from the lanthanide series. The most common lanthanocene complexes contain two cyclopentadienyl anions and an X type ligand, usually hydride or alkyl ligand.

β-carbon elimination is a type of reaction in organometallic chemistry wherein an allyl ligand bonded to a metal center is broken into the corresponding metal-bonded alkyl (aryl) ligand and an alkene. It is a subgroup of elimination reactions. Though less common and less understood than β-hydride elimination, it is an important step involved in some olefin polymerization processes and transition-metal-catalyzed organic reactions.

<span class="mw-page-title-main">Marinella Mazzanti</span> Italian chemist

Marinella Mazzanti is an Italian inorganic chemist specialized in coordination chemistry. She is a professor at EPFL and the head of the group of Coordination Chemistry at EPFL's School of Basic Sciences.

Organotechnetium compounds in organometallic chemistry contain carbon-to-technetium chemical bonds. Organotechnetium chemistry is the science of organotechnetium compounds describing their physical properties, synthesis and reactions. They are most widely used as a radiopharmaceutical imaging agent. Most commonly as Coordination complexes, although organotechnetium radiopharmaceuticals are emerging.

Karsten Meyer is a German inorganic chemist and Chair of Inorganic and General Chemistry at the Friedrich-Alexander University of Erlangen-Nürnberg (FAU). His research involves the coordination chemistry of transition metals as well as uranium coordination chemistry, small molecule activation with these coordination complexes, and the synthesis of new chelating ligands. He is the 2017 recipient of the Elhuyar-Goldschmidt Award of the Spanish Royal Society of Chemistry, the Ludwig-Mond Award of the Royal Society of Chemistry, and the L.A. Chugaev Commemorative Medal of the Russian Academy of Sciences, among other awards. He also serves as an Associate Editor of the journal Organometallics since 2014.

<span class="mw-page-title-main">Paula Diaconescu</span> Inorganic chemist

Paula L. Diaconescu is a Romanian-American chemistry professor at the University of California, Los Angeles. She is known for her research on the synthesis of redox active transition metal complexes, the synthesis of lanthanide complexes, metal-induced small molecule activation, and polymerization reactions. She is a fellow of the American Association for the Advancement of Science.

Phosphanides are chemicals containing the [PH2] anion. This is also known as the phosphino anion or phosphido ligand. The IUPAC name can also be dihydridophosphate(1−).

Suzanne Cathleen Bart an American chemist who is a professor of Inorganic Chemistry at Purdue University. Her group's research focuses on actinide organometallic chemistry, and especially the characterization of low-valent organouranium complexes, actinide complexes with redox-active ligands, and discovery of new reactions that utilize these compounds. Bart's research has applications in the development of carbon-neutral fuel sources and the remediation of polluted sites.

References

  1. "Alumna Jaqueline Kiplinger to receive F. Albert Cotton Award - Department of Chemistry - The University of Utah". chem.utah.edu. Retrieved 2017-06-04.
  2. Ruminski, Ronald; Kiplinger, Jaqueline; Cockcroft, Timothy; Chase, Charles (1989). "Triammineruthenium(II) Complexes Bound with the Novel Bridging Ligand 2,3,5,6-Tetrakis(2- pyridyl)pyrazine (tppz)". Inorganic Chemistry. 28 (2): 370–373. doi:10.1021/ic00301a043.
  3. Ruminski, Ronald; Kiplinger, Jaqueline (1990). "Synthesis and Characterization of Cyanoiron(II) Complexes Bound to the Bridging Ligand Tetrakis(2- pyridyl)-1,4-diazine (tpd)". Inorganic Chemistry. 29 (22): 4581–4584. doi:10.1021/ic00347a051.
  4. Kiplinger, Jaqueline L.; Richmond, Thomas G.; Osterberg, Carolyn E. (1994-03-01). "Activation of Carbon-Fluorine Bonds by Metal Complexes". Chemical Reviews. 94 (2): 373–431. doi:10.1021/cr00026a005. ISSN   0009-2665.
  5. Kiplinger, Jaqueline L.; King, Margaret A.; Fechtenkötter, Andreas; Arif, Atta M.; Richmond, Thomas G. (1996-12-10). "An Investigation of Carbon−Fluorine Bond Functionalization. Versatile Reactivity of Tungsten(II) Fluoride Carbonyl Metallacycles with Alkynes". Organometallics. 15 (25): 5292–5301. doi:10.1021/om960561s. ISSN   0276-7333.
  6. Kiplinger, Jaqueline L.; Richmond, Thomas G. (1996-01-01). "Selective room temperature hydrogenolysis of aromatic fluorocarbons mediated by a low-valent zirconium complex". Chemical Communications (10): 1115–1116. doi:10.1039/CC9960001115. ISSN   1364-548X.
  7. Kiplinger, Jaqueline L.; Morris, David E.; Scott, Brian L.; Burns, Carol J. (2002-07-01). "The First f-Element Ketimido Complex: Synthesis and Characterization of (C5Me5)2U(−NCPh2)2". Organometallics. 21 (15): 3073–3075. doi:10.1021/om020381k. ISSN   0276-7333.
  8. Kiplinger, Jaqueline L.; John, Kevin D.; Morris, David E.; Scott, Brian L.; Burns, Carol J. (2002-10-01). "[(C5Me5)2U(Me)(OTf)]2: A New Reagent for Uranium Metallocene Chemistry. Preparation of the First Actinide Hydrazonato Complexes". Organometallics. 21 (21): 4306–4308. doi:10.1021/om0205804. ISSN   0276-7333.
  9. Kiplinger, Jaqueline L.; Morris, David E.; Scott, Brian L.; Burns, Carol J. (2002-12-01). "Convenient Synthesis, Structure, and Reactivity of (C5Me5)U(CH2C6H5)3: A Simple Strategy for the Preparation of Monopentamethylcyclopentadienyl Uranium(IV) Complexes". Organometallics. 21 (26): 5978–5982. doi:10.1021/om0206610. ISSN   0276-7333.
  10. Monreal, Marisa J.; Wright, Robert J.; Morris, David E.; Scott, Brian L.; Golden, Jeffery T.; Power, Philip P.; Kiplinger, Jaqueline L. (2013-03-11). "Thorium(IV) and Uranium(IV) Halide Complexes Supported by Bulky β-Diketiminate Ligands". Organometallics. 32 (5): 1423–1434. doi:10.1021/om3010965. ISSN   0276-7333.
  11. 1 2 3 Monreal, Marisa J.; Seaman, Lani A.; Goff, George S.; Michalczyk, Ryszard; Morris, David E.; Scott, Brian L.; Kiplinger, Jaqueline L. (2016-03-07). "New Twists and Turns for Actinide Chemistry: Organometallic Infinite Coordination Polymers of Thorium Diazide". Angewandte Chemie International Edition. 55 (11): 3631–3636. doi:10.1002/anie.201510851. ISSN   1521-3773. PMID   26865502.
  12. 1 2 3 Pagano, Justin K.; Dorhout, Jacquelyn M.; Czerwinski, Kenneth R.; Morris, David E.; Scott, Brian L.; Waterman, Rory; Kiplinger, Jaqueline L. (2016-03-14). "Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C5Me5)2U(μ-H)]2". Organometallics. 35 (5): 617–620. doi:10.1021/acs.organomet.6b00091. ISSN   0276-7333. OSTI   1400122.
  13. Browne, Kevin P.; Maerzke, Katie A.; Travia, Nicholas E.; Morris, David E.; Scott, Brian L.; Henson, Neil J.; Yang, Ping; Kiplinger, Jaqueline L.; Veauthier, Jacqueline M. (2016-05-16). "Synthesis, Characterization, and Density Functional Theory Analysis of Uranium and Thorium Complexes Containing Nitrogen-Rich 5-Methyltetrazolate Ligands". Inorganic Chemistry. 55 (10): 4941–4950. doi:10.1021/acs.inorgchem.6b00492. ISSN   0020-1669. PMID   27110650.
  14. Pagano, Justin K.; Dorhout, Jacquelyn M.; Waterman, Rory; Czerwinski, Kenneth R.; Kiplinger, Jaqueline L. (2015-11-26). "Phenylsilane as a safe, versatile alternative to hydrogen for the synthesis of actinide hydrides". Chemical Communications. 51 (98): 17379–17381. doi:10.1039/C5CC06856H. ISSN   1364-548X. PMID   26490094.
  15. 1 2 "Inorganic Chemistry Communications | Vol 77, Pgs 1-82, (March 2017) | ScienceDirect.com". www.sciencedirect.com. Retrieved 2017-06-07.
  16. "Los Alamos chemist elected Fellow of the American Chemical Society".
  17. Energy, Los Alamos National Laboratory, Operated by Los Alamos National Security, LLC, for the U.S. Department of. "Jaqueline L. Kiplinger receives the IUPAC 2017 Distinguished Women in Chemistry award". www.lanl.gov. Retrieved 2017-06-07.
  18. "Distinguished Alumni - Department of Chemistry - the University of Utah".
  19. "F. Albert Cotton Award in Synthetic Inorganic Chemistry - American Chemical Society". American Chemical Society. Retrieved 2017-06-07.
  20. Kiplinger, Jaqueline (Spring–Summer 2014). "News from the Organometallics Subdivision" (PDF). American Chemical Society Division of Inorganic Chemistry: 20–21.
  21. "LANL News: Los Alamos Innovations Take Three R&D 100 Tech Awards".
  22. "Nobel Laureate Signature Award for Graduate Education in Chemistry". American Chemical Society. Retrieved 21 September 2019.