Uranium and thorium complexes of the phosphaethynolate ion
Abstract
New tris-amidinate actinide (Th, U) complexes containing a rare O-bound terminal phosphaethynolate (OCP⁻) ligand were synthesized and fully characterized. The cyanate (OCN⁻) and thiocyanate (SCN⁻) analogs were prepared for comparison and feature a preferential N-coordination to the actinide metals. The Th(amid)3(OCP) complex reacts with Ni(COD)2 to yield the heterobimetallic adduct (amid)3Th(μ-η1(O):η2(C,P)-OCP)Ni(COD) featuring an unprecedented reduced (OCP⁻) bent fragment bridging the two metals.
- Authors:
-
- Lawrence Berkeley National Lab., Berkeley, CA (United States). Chemical Sciences Div.
- Universit´e de Toulouse, Toulouse (France). LPCNO.
- Univ. of Oxford, Oxford (United Kingdom). Dept. of Chemisty.
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1214437
- Grant/Contract Number:
- AC02-05CH11231; NIH S10-RR027172
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 11; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Camp, Clément, Settineri, Nicholas, Lefèvre, Julia, Jupp, Andrew R., Goicoechea, José M., Maron, Laurent, and Arnold, John. Uranium and thorium complexes of the phosphaethynolate ion. United States: N. p., 2015.
Web. doi:10.1039/C5SC02150B.
Camp, Clément, Settineri, Nicholas, Lefèvre, Julia, Jupp, Andrew R., Goicoechea, José M., Maron, Laurent, & Arnold, John. Uranium and thorium complexes of the phosphaethynolate ion. United States. https://doi.org/10.1039/C5SC02150B
Camp, Clément, Settineri, Nicholas, Lefèvre, Julia, Jupp, Andrew R., Goicoechea, José M., Maron, Laurent, and Arnold, John. Sat .
"Uranium and thorium complexes of the phosphaethynolate ion". United States. https://doi.org/10.1039/C5SC02150B. https://www.osti.gov/servlets/purl/1214437.
@article{osti_1214437,
title = {Uranium and thorium complexes of the phosphaethynolate ion},
author = {Camp, Clément and Settineri, Nicholas and Lefèvre, Julia and Jupp, Andrew R. and Goicoechea, José M. and Maron, Laurent and Arnold, John},
abstractNote = {New tris-amidinate actinide (Th, U) complexes containing a rare O-bound terminal phosphaethynolate (OCP⁻) ligand were synthesized and fully characterized. The cyanate (OCN⁻) and thiocyanate (SCN⁻) analogs were prepared for comparison and feature a preferential N-coordination to the actinide metals. The Th(amid)3(OCP) complex reacts with Ni(COD)2 to yield the heterobimetallic adduct (amid)3Th(μ-η1(O):η2(C,P)-OCP)Ni(COD) featuring an unprecedented reduced (OCP⁻) bent fragment bridging the two metals.},
doi = {10.1039/C5SC02150B},
journal = {Chemical Science},
number = 11,
volume = 6,
place = {United States},
year = {Sat Jun 20 00:00:00 EDT 2015},
month = {Sat Jun 20 00:00:00 EDT 2015}
}
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Figures / Tables:
Fig. 1: Left: structure of Re(PCO)(CO)2(triphos) (triphos = MeC(CH3PPh2)3).14 Right: resonance structures for the OCP- anion.
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- Angewandte Chemie International Edition, Vol. 57, Issue 8
The Chemistry of the 2-Phosphaethynolate Anion
journal, November 2018
- Goicoechea, Jose M.; Grützmacher, Hansjörg
- Angewandte Chemie International Edition, Vol. 57, Issue 52
A General Synthesis of Phosphorus- and Arsenic-Containing Analogues of the Thio- and Seleno-cyanate Anions
journal, June 2018
- Tambornino, Frank; Hinz, Alexander; Köppe, Ralf
- Angewandte Chemie International Edition, Vol. 57, Issue 27
Isolation of a TMTAA-Based Radical in Uranium bis-TMTAA Complexes
journal, November 2018
- Hohloch, Stephan; Garner, Mary E.; Booth, Corwin H.
- Angewandte Chemie International Edition, Vol. 57, Issue 49
Cyaarside (CAs − ) and 1,3-Diarsaallendiide (AsCAs 2− ) Ligands Coordinated to Uranium and Generated via Activation of the Arsaethynolate Ligand (OCAs − )
journal, January 2019
- Hoerger, Christopher J.; Heinemann, Frank W.; Louyriac, Elisa
- Angewandte Chemie International Edition, Vol. 58, Issue 6
Terminal Uranium(V/VI) Nitride Activation of Carbon Dioxide and Carbon Disulfide: Factors Governing Diverse and Well-Defined Cleavage and Redox Reactions
journal, January 2017
- Cleaves, Peter A.; Kefalidis, Christos E.; Gardner, Benedict M.
- Chemistry - A European Journal, Vol. 23, Issue 12
A Planar Ti 2 P 2 Core Assembled by Reductive Decarbonylation of − O−C≡P and P−P Radical Coupling
journal, April 2017
- Grant, Lauren N.; Pinter, Balazs; Manor, Brian C.
- Chemistry - A European Journal, Vol. 23, Issue 26
Photolytic and Reductive Activations of 2‐Arsaethynolate in a Uranium–Triamidoamine Complex: Decarbonylative Arsenic‐Group Transfer Reactions and Trapping of a Highly Bent and Reduced Form
journal, October 2019
- Magnall, Rosie; Balázs, Gábor; Lu, Erli
- Chemistry – A European Journal, Vol. 25, Issue 62
Ambient-Temperature Synthesis of 2-Phosphathioethynolate, PCS - , and the Ligand Properties of ECX - (E = N, P; X = O, S) : Ambient-Temperature Synthesis of 2-Phosphathioethynolate
journal, November 2015
- Jupp, Andrew R.; Geeson, Michael B.; McGrady, John E.
- European Journal of Inorganic Chemistry, Vol. 2016, Issue 5
2-Phospha- and 2-Arsaethynolates - Versatile Building Blocks in Modern Synthetic Chemistry: 2-Phospha- and 2-Arsaethynolates - Versatile Building Blocks in Modern Synthetic Chemistry
journal, May 2018
- Weber, Lothar
- European Journal of Inorganic Chemistry, Vol. 2018, Issue 20-21
Electrochemical Oxidation of the Phospha- and Arsaethynolate Anions, PCO - and AsCO -: Electrochemical Oxidation of the Phospha- and Arsaethynolate Anions, PCO - and AsCO -
journal, January 2019
- Tambornino, Frank; Tanner, Eden E. L.; Amin, Hatem M. A.
- European Journal of Inorganic Chemistry, Vol. 2019, Issue 11-12
The heavier pnictogen and chalcogen analogues of isocyanic and cyanic acids and their dimers: A high level ab initio study
journal, June 2019
- Zhang, Zhong; Liu, Chencheng; Tian, Ge
- International Journal of Quantum Chemistry, Vol. 120, Issue 1
Simple access to ionic liquids and organic salts containing the phosphaethynolate (PCO − ) and Zintl (Sb 11 3− ) anions
journal, January 2016
- Jost, Maximilian; Finger, Lars H.; Sundermeyer, Jörg
- Chemical Communications, Vol. 52, Issue 78
The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study
journal, January 2016
- Heift, Dominikus; Benkő, Zoltán; Suter, Riccardo
- Chemical Science, Vol. 7, Issue 9
Facile N-functionalization and strong magnetic communication in a diuranium( v ) bis-nitride complex
journal, January 2019
- Barluzzi, Luciano; Chatelain, Lucile; Fadaei-Tirani, Farzaneh
- Chemical Science, Vol. 10, Issue 12
Finding a soft spot for vanadium: a P-bound OCP ligand
journal, January 2019
- Grant, Lauren N.; Krzystek, J.; Pinter, Balazs
- Chemical Communications, Vol. 55, Issue 42
Salen supported Al–O–CP and Ga–PCO complexes
journal, January 2019
- Mei, Yanbo; Borger, Jaap E.; Wu, Dong-Jun
- Dalton Transactions, Vol. 48, Issue 13
Dioxygen reacts with metal–carbon bonds in thorium dialkyls to produce bis(alkoxides)
journal, January 2019
- Settineri, Nicholas S.; Shiau, Angela A.; Arnold, John
- Dalton Transactions, Vol. 48, Issue 17
Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene
journal, January 2020
- Wilson, Daniel W. N.; Franco, Mauricio P.; Myers, William K.
- Chemical Science, Vol. 11, Issue 3
Structure and magnetism of a tetrahedral uranium( iii ) β-diketiminate complex
journal, January 2020
- Boreen, Michael A.; Gould, Colin A.; Booth, Corwin H.
- Dalton Transactions, Vol. 49, Issue 23
1,3,4-Azadiphospholides as building blocks for scorpionate and bidentate ligands in multinuclear complexes
journal, January 2020
- Suter, Riccardo; Wagner, Mona; Querci, Lorenzo
- Dalton Transactions
Nucleophilic Reactivity of a Nitride-Bridged Diuranium(IV) Complex: CO 2 and CS 2 Functionalization
journal, February 2016
- Falcone, Marta; Chatelain, Lucile; Mazzanti, Marinella
- Angewandte Chemie, Vol. 128, Issue 12
Cyaarside (CAs − ) and 1,3‐Diarsaallendiide (AsCAs 2− ) Ligands Coordinated to Uranium and Generated via Activation of the Arsaethynolate Ligand (OCAs − )
journal, December 2018
- Hoerger, Christopher J.; Heinemann, Frank W.; Louyriac, Elisa
- Angewandte Chemie, Vol. 131, Issue 6
Trapping of a Highly Bent and Reduced Form of 2‐Phosphaethynolate in a Mixed‐Valence Diuranium–Triamidoamine Complex
journal, June 2019
- Magnall, Rosie; Balázs, Gábor; Lu, Erli
- Angewandte Chemie, Vol. 131, Issue 30
Carbon-Nitrogen Bond Cleavage by a Thorium-NHC-bpy Complex
journal, October 2016
- Garner, Mary E.; Hohloch, Stephan; Maron, Laurent
- Angewandte Chemie International Edition, Vol. 55, Issue 44
Photoelectron Spectroscopy and Theoretical Studies of PCSe − , AsCS − , AsCSe − , and NCSe − : Insights into the Electronic Structures of the Whole Family of ECX − Anions (E=N, P, As; X=O, S, Se)
journal, September 2019
- Yuan, Qinqin; Tambornino, Frank; Hinz, Alexander
- Angewandte Chemie International Edition, Vol. 58, Issue 42
A Convenient Synthesis of 1,2,4- and 1,3,4-Azadiphospholes
journal, August 2016
- Suter, Riccardo; Benkő, Zoltán; Grützmacher, Hansjörg
- Chemistry - A European Journal, Vol. 22, Issue 42
Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC-OH Ligand
journal, February 2018
- Srivastava, Ravi; Moneuse, Raphaël; Petit, Julien
- Chemistry - A European Journal, Vol. 24, Issue 17
Transient Dipnictyl Analogues of Acrylamides, R−E=E′−CONR 2 , and a Related Diphosphadigalletane from Na[OCP] and (R 2 N) 2 ECl (E, E′=P, As, Ga)
journal, February 2019
- Borger, Jaap E.; Le Corre, Grégoire; Mei, Yanbo
- Chemistry – A European Journal, Vol. 25, Issue 15
The Rise of Phosphaethynolate Chemistry in Early Transition Metals, Actinides, and Rare‐Earth Complexes
journal, October 2019
- Grant, Lauren N.; Mindiola, Daniel J.
- Chemistry – A European Journal, Vol. 25, Issue 71
(Phosphanyl)phosphaketenes as building blocks for novel phosphorus heterocycles
journal, January 2017
- Hansmann, Max M.; Ruiz, David A.; Liu, Liu (Leo)
- Chemical Science, Vol. 8, Issue 5
1,3,4-Azadiphospholides as building blocks for scorpionate and bidentate ligands in multinuclear complexes
text, January 2020
- Suter, Riccardo; Wagner, Mona K.; Querci, Lorenzo
- ETH Zurich
An Isolable Phosphaethynolatoborane and Its Reactivity
journal, January 2018
- Wilson, Daniel W. N.; Hinz, Alexander; Goicoechea, Jose M.
- Angewandte Chemie, Vol. 130, Issue 8
Isolation of a TMTAA‐Based Radical in Uranium bis‐TMTAA Complexes
journal, October 2018
- Hohloch, Stephan; Garner, Mary E.; Booth, Corwin H.
- Angewandte Chemie, Vol. 130, Issue 49
Unexpected Photodegradation of a Phosphaketenyl-Substituted Germyliumylidene Borate Complex
journal, March 2017
- Xiong, Yun; Yao, Shenglai; Szilvási, Tibor
- Angewandte Chemie International Edition, Vol. 56, Issue 15
Borane-Stabilized Isomeric Dimers of the Phosphaethynolate Anion
journal, October 2017
- Szkop, Kevin M.; Jupp, Andrew R.; Suter, Riccardo
- Angewandte Chemie International Edition, Vol. 56, Issue 45
From As -Zincoarsasilene (LZn-As=SiL′) to Arsaethynolato (As≡C−O) and Arsaketenylido (O=C=As) Zinc Complexes
journal, February 2019
- Ballestero-Martínez, Ernesto; Szilvási, Tibor; Hadlington, Terrance J.
- Angewandte Chemie International Edition, Vol. 58, Issue 11
The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): A mechanistic case study
text, January 2016
- Heift, Dominikus; Benkő, Zoltán; Suter, Riccardo
- ETH Zurich
Facile Access to NaOC≡As and Its Use as an Arsenic Source To Form Germylidenylarsinidene Complexes
journal, May 2017
- Yao, Shenglai; Grossheim, Yves; Kostenko, Arseni
- Angewandte Chemie, Vol. 129, Issue 26
A μ‐Phosphido Diiron Dumbbell in Multiple Oxidation States
journal, October 2019
- Ghosh, Munmun; Cramer, Hanna H.; Dechert, Sebastian
- Angewandte Chemie International Edition, Vol. 58, Issue 40
The 2-Arsaethynolate Anion: Synthesis and Reactivity Towards Heteroallenes
journal, April 2016
- Hinz, Alexander; Goicoechea, Jose M.
- Angewandte Chemie, Vol. 128, Issue 30
A μ‐Phosphido Diiron Dumbbell in Multiple Oxidation States
journal, August 2019
- Ghosh, Munmun; Cramer, Hanna H.; Dechert, Sebastian
- Angewandte Chemie, Vol. 131, Issue 40
Facile Access to NaOC≡As and Its Use as an Arsenic Source To Form Germylidenylarsinidene Complexes
journal, May 2017
- Yao, Shenglai; Grossheim, Yves; Kostenko, Arseni
- Angewandte Chemie International Edition, Vol. 56, Issue 26
Trapping of a Highly Bent and Reduced Form of 2-Phosphaethynolate in a Mixed-Valence Diuranium-Triamidoamine Complex
journal, June 2019
- Magnall, Rosie; Balázs, Gábor; Lu, Erli
- Angewandte Chemie International Edition, Vol. 58, Issue 30
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