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Title: Uranium and thorium complexes of the phosphaethynolate ion

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C5SC02150B· OSTI ID:1214437
 [1];  [1];  [2];  [3];  [3];  [2];  [1]
  1. Lawrence Berkeley National Lab., Berkeley, CA (United States). Chemical Sciences Div.
  2. Universit´e de Toulouse, Toulouse (France). LPCNO.
  3. Univ. of Oxford, Oxford (United Kingdom). Dept. of Chemisty.
+ Show Author Affiliations

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.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; NIH S10-RR027172
OSTI ID:
1214437
Journal Information:
Chemical Science, Vol. 6, Issue 11; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 75 works
Citation information provided by
Web of Science

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Cited By (57)

Carbon-Nitrogen Bond Cleavage by a Thorium-NHC-bpy Complex journal September 2016
Unexpected Photodegradation of a Phosphaketenyl-Substituted Germyliumylidene Borate Complex journal March 2017
Borane-Stabilized Isomeric Dimers of the Phosphaethynolate Anion journal October 2017
Die Chemie des 2-Phosphaethinolat-Anions journal November 2018
A General Synthesis of Phosphorus‐ and Arsenic‐Containing Analogues of the Thio‐ and Seleno‐cyanate Anions journal June 2018
From As ‐Zincoarsasilene (LZn‐As=SiL′) to Arsaethynolato (As≡C−O) and Arsaketenylido (O=C=As) Zinc Complexes journal March 2019
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
Nucleophilic Reactivity of a Nitride-Bridged Diuranium(IV) Complex: CO 2 and CS 2 Functionalization journal February 2016
The 2-Arsaethynolate Anion: Synthesis and Reactivity Towards Heteroallenes journal April 2016
A Monoanionic Arsenide Source: Decarbonylation of the 2-Arsaethynolate Anion upon Reaction with Bulky Stannylenes journal November 2016
2,4,6-Tri(hydroxy)-1,3,5-triphosphinine, P 3 C 3 (OH) 3 : The Phosphorus Analogue of Cyanuric Acid journal December 2016
Synthesis and Reactivity of Nickel-Stabilised μ 2 :η 2 ,η 2 -P 2 , As 2 and PAs Units journal December 2017
A Scandium-Stabilized Diisophosphaethynolate Ligand: [OCPPCO] 4− journal December 2017
An Isolable Phosphaethynolatoborane and Its Reactivity journal January 2018
The Chemistry of the 2-Phosphaethynolate Anion journal November 2018
A General Synthesis of Phosphorus- and Arsenic-Containing Analogues of the Thio- and Seleno-cyanate Anions journal June 2018
Isolation of a TMTAA-Based Radical in Uranium bis-TMTAA Complexes journal November 2018
Cyaarside (CAs − ) and 1,3-Diarsaallendiide (AsCAs 2− ) Ligands Coordinated to Uranium and Generated via Activation of the Arsaethynolate Ligand (OCAs − ) journal January 2019
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
A Planar Ti 2 P 2 Core Assembled by Reductive Decarbonylation of − O−C≡P and P−P Radical Coupling journal April 2017
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
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
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
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
The heavier pnictogen and chalcogen analogues of isocyanic and cyanic acids and their dimers: A high level ab initio study journal June 2019
Simple access to ionic liquids and organic salts containing the phosphaethynolate (PCO − ) and Zintl (Sb 11 3− ) anions journal January 2016
The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study journal January 2016
Facile N-functionalization and strong magnetic communication in a diuranium( v ) bis-nitride complex journal January 2019
Finding a soft spot for vanadium: a P-bound OCP ligand journal January 2019
Salen supported Al–O–CP and Ga–PCO complexes journal January 2019
Dioxygen reacts with metal–carbon bonds in thorium dialkyls to produce bis(alkoxides) journal January 2019
Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene journal January 2020
Structure and magnetism of a tetrahedral uranium( iii ) β-diketiminate complex journal January 2020
1,3,4-Azadiphospholides as building blocks for scorpionate and bidentate ligands in multinuclear complexes journal January 2020
Nucleophilic Reactivity of a Nitride-Bridged Diuranium(IV) Complex: CO 2 and CS 2 Functionalization journal February 2016
Cyaarside (CAs − ) and 1,3‐Diarsaallendiide (AsCAs 2− ) Ligands Coordinated to Uranium and Generated via Activation of the Arsaethynolate Ligand (OCAs − ) journal December 2018
Trapping of a Highly Bent and Reduced Form of 2‐Phosphaethynolate in a Mixed‐Valence Diuranium–Triamidoamine Complex journal June 2019
Carbon-Nitrogen Bond Cleavage by a Thorium-NHC-bpy Complex journal October 2016
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Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC-OH Ligand journal February 2018
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
The Rise of Phosphaethynolate Chemistry in Early Transition Metals, Actinides, and Rare‐Earth Complexes journal October 2019
(Phosphanyl)phosphaketenes as building blocks for novel phosphorus heterocycles journal January 2017
1,3,4-Azadiphospholides as building blocks for scorpionate and bidentate ligands in multinuclear complexes text January 2020
An Isolable Phosphaethynolatoborane and Its Reactivity journal January 2018
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Unexpected Photodegradation of a Phosphaketenyl-Substituted Germyliumylidene Borate Complex journal March 2017
Borane-Stabilized Isomeric Dimers of the Phosphaethynolate Anion journal October 2017
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A μ‐Phosphido Diiron Dumbbell in Multiple Oxidation States journal October 2019
The 2-Arsaethynolate Anion: Synthesis and Reactivity Towards Heteroallenes journal April 2016
A μ‐Phosphido Diiron Dumbbell in Multiple Oxidation States journal August 2019
Facile Access to NaOC≡As and Its Use as an Arsenic Source To Form Germylidenylarsinidene Complexes journal May 2017
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Linked Research (7)

Figures / Tables (7)

Fig. 1(p. 1)figure Fig. 1
Fig. 2(p. 2)figure Fig. 2
Scheme 1(p. 2)figure Scheme 1
Table 1(p. 3)table Table 1
Fig. 3(p. 4)figure Fig. 3
Fig. 4(p. 4)figure Fig. 4
Scheme 2(p. 4)figure Scheme 2

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