Spectroscopic, Magnetic, and Computational Investigations on a Series of Rhenium(III) Cyclopentadienide β-diketiminate Halide and Pseudohalide Complexes
Abstract
Here the low-valent rhenium(I) salt Na[Re(η5-Cp)(BDI)] (BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) was shown to react with various halide and chalcogenolate reagents, leading to the isolation of a series of rhenium(III)-halide and -pseudohalide complexes: Re(X)(η5-Cp)(BDI) (1-X, X = F, Cl, Br, I; 2, X = OTf) and Re(ER)(η5-Cp)(BDI) (3-ER, ER = SBn, SeBn, TePh). The 1H NMR spectra of these complexes displayed sharp resonances shifted several ppm from typical diamagnetic regions, as well as distinct chemical shift trends down both the halide (with the exception of F) and chalcogenolate series, with both Cp and BDI backbone peaks moving downfield with increasing atomic number. Subsequent magnetic susceptibility measurements of the rhenium(III) halides 1-Cl, 1-Br, and 1-I indicated that these complexes display temperature-independent paramagnetism (TIP), with χTIPvalues of 7.41(44) × 10-4 to 1.50(51) × 10-3cm3mol-1. Multireference complete active space self-consistent field (CASSCF) computations incorporating spin-orbit state mixing revealed small energy separations (1.7-3.0 kcal/mol) between thermally isolated ground states and the first excited spin-orbit states for the rhenium halides, confirming that low-lying excited states are responsible for the observed TIP behavior.
- Authors:
-
[1];
[3];
[1];
[2];
[3];
[1]
- University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- University of Toulouse (France)
- University of California, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Science Foundation (NSF); National Institutes of Health (NIH)
- OSTI Identifier:
- 2326974
- Grant/Contract Number:
- AC02-05CH11231; CHE-1465188; CHE-1954612; S10OD024998; CHE-1800252
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Organometallics
- Additional Journal Information:
- Journal Volume: 41; Journal Issue: 22; Journal ID: ISSN 0276-7333
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Ouellette, Erik T., Amaro Estrada, Jorge Ivan, Lussier, Daniel J., Chakarawet, Khetpakorn, Lohrey, Trevor D., Maron, Laurent, Bergman, Robert G., and Arnold, John. Spectroscopic, Magnetic, and Computational Investigations on a Series of Rhenium(III) Cyclopentadienide β-diketiminate Halide and Pseudohalide Complexes. United States: N. p., 2021.
Web. doi:10.1021/acs.organomet.1c00516.
Ouellette, Erik T., Amaro Estrada, Jorge Ivan, Lussier, Daniel J., Chakarawet, Khetpakorn, Lohrey, Trevor D., Maron, Laurent, Bergman, Robert G., & Arnold, John. Spectroscopic, Magnetic, and Computational Investigations on a Series of Rhenium(III) Cyclopentadienide β-diketiminate Halide and Pseudohalide Complexes. United States. https://doi.org/10.1021/acs.organomet.1c00516
Ouellette, Erik T., Amaro Estrada, Jorge Ivan, Lussier, Daniel J., Chakarawet, Khetpakorn, Lohrey, Trevor D., Maron, Laurent, Bergman, Robert G., and Arnold, John. Fri .
"Spectroscopic, Magnetic, and Computational Investigations on a Series of Rhenium(III) Cyclopentadienide β-diketiminate Halide and Pseudohalide Complexes". United States. https://doi.org/10.1021/acs.organomet.1c00516. https://www.osti.gov/servlets/purl/2326974.
@article{osti_2326974,
title = {Spectroscopic, Magnetic, and Computational Investigations on a Series of Rhenium(III) Cyclopentadienide β-diketiminate Halide and Pseudohalide Complexes},
author = {Ouellette, Erik T. and Amaro Estrada, Jorge Ivan and Lussier, Daniel J. and Chakarawet, Khetpakorn and Lohrey, Trevor D. and Maron, Laurent and Bergman, Robert G. and Arnold, John},
abstractNote = {Here the low-valent rhenium(I) salt Na[Re(η5-Cp)(BDI)] (BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) was shown to react with various halide and chalcogenolate reagents, leading to the isolation of a series of rhenium(III)-halide and -pseudohalide complexes: Re(X)(η5-Cp)(BDI) (1-X, X = F, Cl, Br, I; 2, X = OTf) and Re(ER)(η5-Cp)(BDI) (3-ER, ER = SBn, SeBn, TePh). The 1H NMR spectra of these complexes displayed sharp resonances shifted several ppm from typical diamagnetic regions, as well as distinct chemical shift trends down both the halide (with the exception of F) and chalcogenolate series, with both Cp and BDI backbone peaks moving downfield with increasing atomic number. Subsequent magnetic susceptibility measurements of the rhenium(III) halides 1-Cl, 1-Br, and 1-I indicated that these complexes display temperature-independent paramagnetism (TIP), with χTIPvalues of 7.41(44) × 10-4 to 1.50(51) × 10-3cm3mol-1. Multireference complete active space self-consistent field (CASSCF) computations incorporating spin-orbit state mixing revealed small energy separations (1.7-3.0 kcal/mol) between thermally isolated ground states and the first excited spin-orbit states for the rhenium halides, confirming that low-lying excited states are responsible for the observed TIP behavior.},
doi = {10.1021/acs.organomet.1c00516},
journal = {Organometallics},
number = 22,
volume = 41,
place = {United States},
year = {Fri Nov 12 00:00:00 EST 2021},
month = {Fri Nov 12 00:00:00 EST 2021}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Regio- and Stereoselective Nucleophilic Substitutions of Chiral Allylic Alcohol Rhenium Complexes
journal, November 1998
- Legoupy, Stéphanie; Crévisy, Christophe; Guillemin, Jean-Claude
- Chemistry - A European Journal, Vol. 4, Issue 11
Mechanism of Chemical and Electrochemical N 2 Splitting by a Rhenium Pincer Complex
journal, May 2018
- Lindley, Brian M.; van Alten, Richt S.; Finger, Markus
- Journal of the American Chemical Society, Vol. 140, Issue 25
Temperature dependence of contact and dipolar NMR chemical shifts in paramagnetic molecules
journal, February 2015
- Martin, Bob; Autschbach, Jochen
- The Journal of Chemical Physics, Vol. 142, Issue 5
Metal-Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen
journal, December 2018
- Schendzielorz, Florian; Finger, Markus; Abbenseth, Josh
- Angewandte Chemie International Edition, Vol. 58, Issue 3
Piano-stool complexes of the CpML4 type
journal, January 1982
- Kubacek, Pavel; Hoffmann, Roald; Havlas, Zdenek
- Organometallics, Vol. 1, Issue 1
Syntheses, Structures and Reactivities of [CpTc(CO) 3 X] + and [CpRe(CO) 3 X] +
journal, September 2008
- Zobi, Fabio; Spingler, Bernhard; Alberto, Roger
- European Journal of Inorganic Chemistry, Vol. 2008, Issue 27
Bis(cyclopentadienyl)rhenium(III)chlorid: Kristallstruktur, Eigenschaften und Reaktivität; Darstellung und Charakterisierung von Cp3Re und Cp2ReH
journal, May 1991
- Apostolidis, Christos; Kanellakopulos, Basil; Maier, Ralph
- Journal of Organometallic Chemistry, Vol. 409, Issue 1-2
Appreciably bent sp carbon chains: synthesis, structure, and protonation of organometallic 1,3,5-triynes and 1,3,5,7-tetraynes of the formula (η5-C5Me5)Re(NO)(PPh3)((CC)n-p-C6H4Me)
journal, April 1999
- Dembinski, Roman; Lis, Tadeusz; Szafert, Slawomir
- Journal of Organometallic Chemistry, Vol. 578, Issue 1-2
The importance of inter-molecular forces in crystal structure analysis: Solid state study of the diag-to-lat isomerization of (η5-C5H4Me)Re(CO)2Br2
journal, January 1998
- Boeyens, Jan C. A.; Cheng, Lin; Coville, Neil J.
- Journal of Chemical Crystallography, Vol. 28, Issue 3, p. 185-191
Reduction pathways in lateral and diagonal (.eta.5-C5Me5)Re(CO)2Br2. Synthesis, structure, and reactivity of [(.eta.5-C5Me5)Re(CO)2Br-]
journal, May 1990
- Nunn, Christine M.; Cowley, Alan H.; Lee, Sang Woo
- Inorganic Chemistry, Vol. 29, Issue 11
A mechanochemical strategy for oxidative addition: remarkable yields and stereoselectivity in the halogenation of organometallic Re( i ) complexes
journal, January 2014
- Hernández, José G.; Macdonald, Neil A. J.; Mottillo, Cristina
- Green Chem., Vol. 16, Issue 3
{Re III Cl 3 } Core Complexes with Bifunctional Single Amino Acid Chelates
journal, November 2002
- Banerjee, Sangeeta Ray; Wei, Lihui; Levadala, Murali K.
- Inorganic Chemistry, Vol. 41, Issue 22
Synthesis and characterisation of half-sandwich tantalum compounds in oxidation states (I)–(V): tertiary phosphine, acetylene, butadiene, carbonyl, and oxo derivatives. X-Ray crystal structures of [Ta(C 5 Me 5 )Cl 3 (PMe 3 )] and [Ta(C 5 Me 5 )Cl 2 (CO) 2 (PMe 3 )]
journal, January 1990
- Gibson, Vernon C.; Kee, Terence P.; Clegg, William
- J. Chem. Soc., Dalton Trans., Issue 11
Magnetic susceptibilities of some rhenium(III) and osmium(IV) halide complexes; preparation of some new d 4 complexes
journal, January 1971
- Gunz, H. P.; Leigh, G. J.
- Journal of the Chemical Society A: Inorganic, Physical, Theoretical
Syntheses and structural analyses of chiral rhenium containing amines of the formula (η5-C5H5)Re(NO)(PPh3)((CH2)nNRR′) (n=0, 1)
journal, February 2010
- Seidel, Sabine N.; Prommesberger, Markus; Eichenseher, Sandra
- Inorganica Chimica Acta, Vol. 363, Issue 3
Dinitrogen Reduction to Ammonium at Rhenium Utilizing Light and Proton-Coupled Electron Transfer
journal, November 2019
- Bruch, Quinton J.; Connor, Gannon P.; Chen, Chun-Hsing
- Journal of the American Chemical Society, Vol. 141, Issue 51
Dinuclear and Mononuclear Rhenium Coordination Compounds upon Employment of a Schiff-Base Triol Ligand: Structural, Magnetic, and Computational Studies
journal, June 2019
- Kalofolias, Dimitris A.; Weselski, Marek; Siczek, Milosz
- Inorganic Chemistry, Vol. 58, Issue 13
Multiple bonds between main-group elements and transition metals. 48. Synthesis and structural characterization of trioxo(.eta.5-ethyltetramethylcyclopentadienyl)rhenium, a half-sandwich complex of heptavalent rhenium
journal, April 1988
- Okuda, Jun; Herdtweck, Eberhardt; Herrmann, Wolfgang A.
- Inorganic Chemistry, Vol. 27, Issue 7
Organometallic oxides: the example of trioxo-(η5-pentamethylcyclopentadienyl)rhenium(VII)
journal, January 1987
- Herrmann, Wolfgang A.; Herdtweck, Eberhardt; Flöel, Martina
- Polyhedron, Vol. 6, Issue 6
Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation
journal, May 2009
- Booth, Corwin H.; Walter, Marc D.; Kazhdan, Daniel
- Journal of the American Chemical Society, Vol. 131, Issue 18
Olefin-Supported Rhenium(III) Terminal Oxo Complexes Generated by Nucleophilic Addition to a Cyclopentadienyl Ligand
journal, October 2017
- Lohrey, Trevor D.; Bergman, Robert G.; Arnold, John
- Angewandte Chemie International Edition, Vol. 56, Issue 45
Solid-State Reactivity and Single-Crystal Structure Studies. The Case of diag − lat Isomerization in [Re(η 5 -C 5 H 4 Me)(CO)(P(OPh 3 )Br 2 ] and [Re(η 5 -C 5 H 4 t Bu)(CO) 2 Br 2 ]
journal, May 2000
- Smith, Jeremy M.; Cheng, Lin; Coville, Neil J.
- Organometallics, Vol. 19, Issue 13
Electronic Structures of Rhenium(II) β-Diketiminates Probed by EPR Spectroscopy: Direct Comparison of an Acceptor-Free Complex to Its Dinitrogen, Isocyanide, and Carbon Monoxide Adducts
journal, July 2020
- Lohrey, Trevor D.; Rao, Guodong; Small, David W.
- Journal of the American Chemical Society, Vol. 142, Issue 32
Novel rhenium(III) complexes with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine: X-ray structures and DFT calculations for [ReCl3(OPPh3)(dppt)] and [ReCl3(PPh3)(dppt)] complexes
journal, September 2007
- Machura, B.; Kruszynski, R.; Kusz, J.
- Polyhedron, Vol. 26, Issue 15
The biomedical chemistry of technetium and rhenium
journal, January 1998
- R. Dilworth, Jonathan; J. Parrott, Suzanne
- Chemical Society Reviews, Vol. 27, Issue 1
σ or π? Bonding interactions in a series of rhenium metallotetrylenes
journal, January 2021
- Ouellette, Erik T.; Carpentier, Ambre; Joseph Brackbill, I.
- Dalton Transactions, Vol. 50, Issue 6
Ab initio molecular calculations including spin-orbit coupling. II. Molecular test on the InH molecule and application to the g states of the Ar2* excimer
journal, November 1983
- Teichteil, C.; Spiegelmann, F.
- Chemical Physics, Vol. 81, Issue 3
Coordination chemistry of di-2-pyridylketone. Synthesis, spectroscopic investigations, X-ray studies and DFT calculations of Re(III) and Re(V) complexes
journal, September 2009
- Machura, B.; Mroziński, J.; Kruszynski, R.
- Polyhedron, Vol. 28, Issue 14
1H NMR study of monomeric chloro-rhenium(III) complexes with triarylphosphines and nitriles
journal, September 1995
- Pearson, Céline; Beauchamp, AndréL.
- Inorganica Chimica Acta, Vol. 237, Issue 1-2
Second-order paramagnetic rhenium(III) complexes: solid-state structure and assignment of the carbon-13 magnetic resonance spectra in solution
journal, January 1996
- Mitsopoulou, Christiana A.; Mahieu, Nathalie; Motevalli, Majid
- Journal of the Chemical Society, Dalton Transactions, Issue 24
602. The magnetic properties of some d 3-complexes
journal, January 1961
- Figgis, B. N.; Lewis, J.; Mabbs, F. E.
- Journal of the Chemical Society (Resumed)
H 2 Activation and Direct Access to Terminal Nitride and cyclo -P 3 Complexes by an Acceptor-Free Rhenium(II) β-Diketiminate
journal, September 2019
- Lohrey, Trevor D.; Rao, Guodong; Britt, R. David
- Inorganic Chemistry, Vol. 58, Issue 19
Towards molecular imaging and treatment of disease with radionuclides: the role of inorganic chemistry
journal, January 2006
- Blower, Phil
- Dalton Transactions, Issue 14
A Thorium Chalcogenolate Series Generated by Atom Insertion into Thorium–Carbon Bonds
journal, April 2017
- Settineri, Nicholas S.; Garner, Mary E.; Arnold, John
- Journal of the American Chemical Society, Vol. 139, Issue 17
Uranium(VI) Bis(imido) Chalcogenate Complexes: Synthesis and Density Functional Theory Analysis
journal, March 2009
- Spencer, Liam P.; Yang, Ping; Scott, Brian L.
- Inorganic Chemistry, Vol. 48, Issue 6
Nuclear magnetic resonance spectra of d 4-complexes of rhenium(III) and osmium(IV) with phosphine and arsine ligands
journal, January 1969
- Randall, E. W.; Shaw, D.
- Journal of the Chemical Society A: Inorganic, Physical, Theoretical
A Uranium Tri-Rhenium Triple Inverse Sandwich Compound
journal, March 2019
- Boreen, Michael A.; Lohrey, Trevor D.; Rao, Guodong
- Journal of the American Chemical Society, Vol. 141, Issue 13
The preparation and reactions of trihaolgeno(alkanonitrile)bis(triphenylphosphine)rhenium(III) complexes
journal, January 1967
- Rouschias, G.; Wilkinson, G.
- Journal of the Chemical Society A: Inorganic, Physical, Theoretical
Ab initio molecular calculations including spin-orbit coupling. I. Method and atomic tests
journal, November 1983
- Teichteil, Christian; Pelissier, Michel; Spiegelmann, Fernand
- Chemical Physics, Vol. 81, Issue 3
Syntheses, x-ray structures, and cis-trans isomerism of (pentamethylcyclopentadienyl)dicarbonylrhenium dihalides (.eta.-C5Me5)Re(CO)2X2 (X = Cl, Br, I)
journal, January 1986
- Einstein, Frederick W. B.; Klahn-Oliva, A. Hugo; Sutton, Derek
- Organometallics, Vol. 5, Issue 1
Crystal and molecular structure of a perfluoropropyl complex of molybdenum: .pi.-C5H5Mo(CO)3C3F7
journal, June 1967
- Churchill, Melvyn R.; Fennessey, James P.
- Inorganic Chemistry, Vol. 6, Issue 6
A New Family of Chelating Diphosphines with Transition-Metal and Carbon Stereocenters in the Backbone: A Second-Generation Rhenium-Containing System
journal, August 2002
- Kromm, Klemenz; Hampel, Frank; Gladysz, J. A.
- Organometallics, Vol. 21, Issue 20
Synthesis, spectroscopic characterization, X-ray structure and DFT calculations of rhenium(III) complex with 1-isoquinolinyl phenyl ketone
journal, April 2008
- Machura, B.; Kruszynski, R.; Mroziński, J.
- Polyhedron, Vol. 27, Issue 6
Heterotetrametallic Re–Zn–Zn–Re Complex Generated by an Anionic Rhenium(I) β-Diketiminate
journal, December 2018
- Lohrey, Trevor D.; Maron, Laurent; Bergman, Robert G.
- Journal of the American Chemical Society, Vol. 141, Issue 2
Rhenium-Containing Phosphorus Donor Ligands for Palladium-Catalyzed Suzuki Cross-Coupling Reactions: A New Strategy for High-Activity Systems
journal, December 2004
- Eichenseher, Sandra; Delacroix, Olivier; Kromm, Klemenz
- Organometallics, Vol. 24, Issue 2
Electronic and Spin-State Effects on Dinitrogen Splitting to Nitrides in a Rhenium Pincer System
journal, April 2021
- Weber, Jeremy E.; Hasanayn, Faraj; Fataftah, Majed
- Inorganic Chemistry, Vol. 60, Issue 9
Photochemical Reactions of [(η 5 ‐C 5 R 5 )Re(CO) 3 ] (R = Me or H) with Aryl Halides in Benzene: Stoichiometric Formation of Biphenyl
journal, October 2014
- Zhu, Bolin; Huang, Xinwei; Hao, Xiaoting
- European Journal of Inorganic Chemistry, Vol. 2014, Issue 34
Olefin Metatheses in Metal Coordination Spheres: Versatile New Strategies for the Construction of Novel Monohapto or Polyhapto Cyclic, Macrocyclic, Polymacrocyclic, and Bridging Ligands
journal, September 2001
- Ruwwe, Johannes; Martín-Alvarez, José Miguel; Horn, Clemens R.
- Chemistry - A European Journal, Vol. 7, Issue 18
Controlling dinitrogen functionalization at rhenium through alkali metal ion pairing
journal, January 2019
- Lohrey, Trevor D.; Bergman, Robert G.; Arnold, John
- Dalton Transactions, Vol. 48, Issue 48
Dinitrogen Splitting and Functionalization in the Coordination Sphere of Rhenium
journal, May 2014
- Klopsch, Isabel; Finger, Markus; Würtele, Christian
- Journal of the American Chemical Society, Vol. 136, Issue 19
Synthesis, crystal structure and magnetic properties of the complex [ReCl 3 (tppz)]·MeCN
journal, January 2015
- Palion-Gazda, J.; Gryca, I.; Machura, B.
- RSC Advances, Vol. 5, Issue 123
Two novel rhenium complexes derived from [ReO(OMe)Cl2(dpphen)] – Synthesis, crystal structure, spectroscopic and magnetic properties
journal, February 2011
- Machura, B.; Wolff, M.; Gryca, I.
- Polyhedron, Vol. 30, Issue 2
Synthesis, structure, and dynamic behavior of rhenium sulfide and sulfoxide complexes of the formula [(.eta.5-C5H5)Re(NO)(L)(XRR')]+X'- (X = S, SO)
journal, July 1991
- Quiros Mendez, N.; Arif, Atta M.; Gladysz, J. A.
- Organometallics, Vol. 10, Issue 7
Synthesis, structure, and reactivity of stable alkyl and aryl iodide complexes of the formula [(.eta.5-C5H5(Re(NO)(PPh3)(IR)]+BF4-
journal, June 1989
- Winter, Charles H.; Veal, William R.; Garner, Charles M.
- Journal of the American Chemical Society, Vol. 111, Issue 13
Synthesis and Reactivity of Chromium Cyclopentadienyl β-Diketiminato Compounds
journal, March 2004
- Doherty, Jayne C.; Ballem, Katherine H. D.; Patrick, Brian O.
- Organometallics, Vol. 23, Issue 7