skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Insertion, protonolysis and photolysis reactivity of a thorium monoalkyl amidinate complex

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C7SC05328B· OSTI ID:1421572
ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry, University of California, Berkeley, USA, Chemical Sciences Division
+ Show Author Affiliations

The reactivity of the thorium monoalkyl complex Th(CH2SiMe3)(BIMA)3[1, BIMA = MeC(NiPr)2] with various small molecules is described. While steric congestion prohibits the insertion of N,N'-diisopropylcarbodiimide into the Th-C bond in 1, the first thorium tetrakis(amidinate) complex, Th(BIMA)4 (2), is synthesized via an alternative salt metathesis route. Insertion of p-tolyl azide leads to the triazenido complex Th[(p-tolyl)NNN(CH2SiMe3)-κ2 N1,2] (BIMA)3(3), which then undergoes thermal decomposition to the amido species Th[(p-tolyl)N(SiMe3)](BIMA)3 (4). The reaction of 1 with 2,6-dimethylphenylisocyanide results in the thorium iminoacyl complex Th[η2-(CN)-2,6-Me2-C6H3(CH2SiMe3)](BIMA)3 (5), while the reaction with isoelectronic CO leads to the products Th[OC(CH2)SiMe3](BIMA)3 (6) and Th[OC(NiPr)C(CH2SiMe3)(C(Me)N(iPr))O-κ2O,O'](BIMA)2 (7), the latter being the result of CO coupling and insertion into an amidinate ligand. Protonolysis is achieved with several substrates, producing amido (9), aryloxide (10), phosphido (11a,b), acetylide (12), and cationic (13) complexes. Ligand exchange with 9-borabicyclo[3.3.1]nonane (9-BBN) results in formation of the thorium borohydride complex (BIMA)3Th(μ-H)2[B(C8H14)] (14). Complex 1 also reacts under photolytic conditions to eliminate SiMe4 and produce Th(BIMA)2(BIMA*) [15, BIMA* = (iPr)NC(CH2)N(iPr)], featuring a rare example of a dianionic amidinate ligand. Complexes 2, 3, 5, 6, 11a, and 12-15 were characterized by 1H and 13C{1H} NMR spectroscopy, FTIR, EA, melting point and X-ray crystallography. All other complexes were identified by one or more of these spectroscopic techniques.A tris-amidinate thorium monoalkyl complex facilitates new small molecule reactivity and eliminates SiMe4 under photolytic conditions to generate a mixed amidinate dimer.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1421572
Alternate ID(s):
OSTI ID: 1465421
Journal Information:
Chemical Science, Journal Name: Chemical Science Vol. 9 Journal Issue: 10; ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)Copyright Statement
Country of Publication:
United Kingdom
Language:
English
Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

References (97)

Single and Double Alkyl Abstraction from a Bis(anilido)xanthene Thorium(IV) Dibenzyl Complex: Isolation of an Organothorium Cation and a Thorium Dication journal January 2008
Non-least-motion potential surfaces. Dimerization of methylenes and nitroso compounds journal March 1970
Alkyl Complexes of Group 4 Metals Containing a Tridentate-Linked Amido−Cyclopentadienyl Ligand:  Synthesis, Structure, and Reactivity Including Ethylene Polymerization Catalysis journal December 1998
Synthesis and characterization of bis(pentamethylcyclopentadienyl)uranium(IV) and -thorium(IV) compounds containing the bis(trimethylsilyl)phosphide ligand journal March 1993
Intra- and intermolecular organoactinide carbon-hydrogen activation pathways. Formation, properties, and reactions of thoracyclobutanes journal December 1982
Indirect Nonbonded Nuclear Spin–Spin Coupling: A Guide for the Recognition and Understanding of “Through-Space” NMR J Constants in Small Organic, Organometallic, and Coordination Compounds journal February 2014
Bis(pentamethylcyclopentadienyl)actinide alkyls: facile activation of carbon monoxide, carbon-carbon double bond formation, and the production of unusual oxygen-bonded migratory insertion products journal October 1978
Importance of Energy Level Matching for Bonding in Th 3+ -Am 3+ Actinide Metallocene Amidinates, (C 5 Me 5 ) 2 [ i PrNC(Me)N i Pr]An journal November 2010
First Annelated Azaphosphole-Ferrocenes: Synthetic Pathways and Structures journal August 2012
Tris(.eta.5-cyclopentadienyl)alkyl and -alkenyl compounds of thorium(IV) journal February 1976
Alkyne Cycloaddition to a Titanocene Oxide as a Route to Cyclopentadienyl Modification journal May 2014
Synthesis and reactivity of tantalum corrole complexes journal January 2017
Selective Dehydrocoupling of Phosphines by Triamidoamine Zirconium Catalysts journal May 2007
Reductive Elimination of Diphosphine from a Thorium–NHC–Bis(phosphido) Complex journal May 2017
Insertion of t BuNC into thorium–phosphorus and thorium–arsenic bonds: phosphaazaallene and arsaazaallene moieties in f element chemistry journal January 2016
Carbon monoxide activation by organoactinides. A comparative synthetic, thermodynamic, kinetic, and mechanistic investigation of migratory carbon monoxide insertion into actinide-carbon and actinide-hydrogen bonds to yield .eta.2-acyls and .eta.2-formyls journal November 1984
Recent developments in actinide–ligand multiple bonding journal January 2013
NMR of boron compounds journal September 1969
sp3 versus sp2 C–H bond activation chemistry of 2-picoline by Th(IV) and U(IV) metallocene complexes journal October 2007
Chloro-, methyl-, and (tetrahydroborato)tris((hexamethyldisilyl)amido)thorium(IV) and uranium(IV). Crystal structure of (tetrahydroborato)tris((hexamethyldisilyl)amido)thorium(IV) journal May 1979
Olefin-Supported Rhenium(III) Terminal Oxo Complexes Generated by Nucleophilic Addition to a Cyclopentadienyl Ligand journal October 2017
Actinide-carbon bonds: insertion reactions of carbon monoxide, tert-butyl isocyanide, and tert-butyl cyanide into [(Me3Si)2N]2MCH2Si(Me)2NSiMe3 journal July 1981
Synthesis and Insertion Chemistry of Monoalkyl and Monoaryl Uranium(IV) Heteroleptic Metallocene Complexes journal October 2009
Synthesizing Multidentate Ferrocenylphosphines: A Powerful Route to Dissymmetrically Tri-Substituted Ferrocenes. X-ray Structure and 13 C NMR of a Diaryl–Alkyl-phosphino Ferrocene journal October 2004
In Pursuit of Homoleptic Actinide Alkyl Complexes journal June 2012
Synthesis, structure and molecular dynamics of η 2 -iminoacyl compounds [Cp(ArO)Zr(η 2 -Bu t NCCH 2 Ph)(CH 2 Ph)] and [Cp(ArO)Zr(η 2 -Bu t NCCH 2 Ph) 2 ] journal January 2002
Synthesis and characterization of bis(diphenylphosphido)bis(pentamethylcyclopentadienyl)thorium(IV), [(.eta.5-C5(CH3)5]2Th(PPh2)2 journal January 1986
A New Supporting Ligand in Actinide Chemistry Leads to Reactive Bis(NHC)borate-Supported Thorium Complexes journal August 2016
Group Transfer from Nickel Imido, Phosphinidene, and Carbene Complexes to Ethylene with Formation of Aziridine, Phosphirane, and Cyclopropane Products journal November 2003
Syntheses and crystal structures of the tetrakis(methyltrihydroborato) compounds of zirconium(IV), thorium(IV), uranium(IV), and neptunium(IV) journal August 1983
Isolation of the First d0 Metalloxy Ketene Complexes via "Double Insertion" of Carbon Monoxide into Thorium-Silicon Bonds journal March 1995
Hydrogen Activation by an Intramolecular Boron Lewis Acid/Zirconocene Pair journal July 2012
Oligomerization and Cross-Oligomerization of Terminal Alkynes Catalyzed by Organoactinide Complexes journal April 1999
Selective oxidation of organoboranes with anhydrous trimethylamine N-oxide journal April 1986
Systematic Studies of Early Actinide Complexes:  Thorium(IV) Fluoroketimides journal April 2007
A synthetic and mechanistic study of oxycarbene-like coupling reaction patterns of actinide .eta.2-acyl complexes with carbon monoxide and isocyanides journal January 1986
A Homoleptic Uranium(III) Tris(aryl) Complex journal December 2016
A Thorium Chalcogenolate Series Generated by Atom Insertion into Thorium–Carbon Bonds journal April 2017
Uranium( iii ) and thorium( iv ) alkyl complexes as potential starting materials journal January 2016
Oligomerization of Metal-Oxygen Bonds in Thorium Alkoxide Chemistry: X-ray Crystal Structures of Th4(O-i-Pr)16(py)2 and Th2(OCHEt2)8(py)2 journal August 1994
Synthesis and structure of two crystalline forms of (cyclooctatetraene)thorium(IV) dichloride-bis(tetrahydrofuran) journal September 1980
C–F sp 2 bond functionalization mediated by niobium complexes journal January 2015
Experimental and Theoretical ab I nitio Study of the 13 C− 13 C Spin−Spin Coupling and 1 H and 13 C Shielding Tensors in Ethane, Ethene, and Ethyne journal April 1998
The Renaissance of Non-Aqueous Uranium Chemistry journal June 2015
Catalytic Hydrosilylation of Terminal Alkynes Promoted by Organoactinides journal November 1999
Thorium Triamidoamine Complexes: Synthesis of an Unusual Dinuclear Tuck-in–Tuck-over Thorium Metallacycle Featuring the Longest Known Thorium−σ-Alkyl Bond journal November 2014
Carbon-hydrogen activation mechanisms and regioselectivity in the cyclometalation reactions of bis(pentamethylcyclopentadienyl)thorium dialkyl complexes journal January 1986
Synthesis and Properties of a Fifteen-Coordinate Complex: The Thorium Aminodiboranate [Th(H3BNMe2BH3)4] journal March 2010
Is Thorium a d Transition Metal or an Actinide? An Answer from a DFT Study of the Reaction between Pyridine N -Oxide and Cp 2 M(CH 3 ) 2 with M = Zr, Th, and U journal February 2009
Photochemical synthesis of low-valent organothorium complexes. Evidence for photoinduced .beta.-hydride elimination journal March 1977
Ligand steric bulk: A neglected factor in the formation of CrCr supershort contacts journal November 1993
Manipulation of organoactinide coordinative unsaturation and stereochemistry. Properties of chelating bis(polymethylcyclopentadienyl) hydrocarbyls and hydrides journal May 1984
Lanthanide-Imido Complexes and Their Reactions with Benzonitrile journal January 2005
The Reactivity Patterns of Low-Coordinate Iron−Hydride Complexes journal May 2008
Double carbonylation of actinide bis(cyclopentadienyl) complexes. Experimental and theoretical aspects journal July 1986
Thorium Metallacycle Facilitates Catalytic Alkyne Hydrophosphination journal September 2017
Thorium(IV) and Uranium(IV) trans -Calix[2]benzene[2]pyrrolide Alkyl and Alkynyl Complexes: Synthesis, Reactivity, and Electronic Structure journal September 2017
A comparative study of the reactivity of Zr(IV), Hf(IV) and Th(IV) metallocene complexes: Thorium is not a Group IV metal after all journal October 2007
Carbon monoxide and carbon dioxide insertion chemistry of f-block N-heterocyclic carbene complexes journal January 2013
Divergent Pathways Involving 1,3-Dipolar Addition and N−N Bond Splitting of an Organic Azide across a Zirconium Methylidene journal January 2018
A New Mode of Reactivity for Pyridine N -Oxide:  C−H Activation with Uranium(IV) and Thorium(IV) Bis(alkyl) Complexes journal February 2005
Diamine Bis(phenolate) as Supporting Ligands in Organoactinide(IV) Chemistry. Synthesis, Structural Characterization, and Reactivity of Stable Dialkyl Derivatives journal December 2012
Insertion Reactivity of CO 2 , PhNCO, Me 3 CC≡N, and Me 3 CN≡C with the Uranium−Alkynyl Bonds in (C 5 Me 5 ) 2 U(C≡CPh) 2 journal February 2010
Insertion of Carbodiimides and Organic Azides into Actinide−Carbon Bonds journal June 2009
Recent Developments in Synthesis and Structural Chemistry of Nonaqueous Actinide Complexes journal October 2012
Mechanistic study of photoinduced .beta.-hydride elimination. The facile photochemical synthesis of low-valent thorium and uranium organometallics journal April 1982
Uranium and thorium complexes of the phosphaethynolate ion journal January 2015
New supporting ligands in actinide chemistry: tetramethyltetraazaannulene complexes with thorium and uranium journal January 2017
Arene-ligated heteroleptic terphenolate complexes of thorium journal January 2014
Towards uranium catalysts journal September 2008
Formation of a Bridging Phosphinidene Thorium Complex journal November 2015
Stabilization of M IV = Ti, Zr, Hf, Ce, and Th using a selenium bis(phenolate) ligand journal January 2015
Bis(permethylindenyl) Complexes of Thorium:  Synthesis, Structure, and Reactivity journal July 2001
Synthesis, structure, and reactivity of crystalline molecular complexes of the {[C 5 H 3 (SiMe 3 ) 2 ] 3 Th} 1− anion containing thorium in the formal +2 oxidation state journal January 2015
Synthesis and characterization of thorium tert-butoxide complexes: x-ray crystal structures of Th(O-tert-Bu)4(py)2 and NaTh2(O-tert-Bu)9 journal April 1993
Insertion, Isomerization, and Cascade Reactivity of the Tethered Silylalkyl Uranium Metallocene (η 5 -C 5 Me 4 SiMe 2 CH 2 -κ C ) 2 U journal March 2011
The Bis Metallacyclic Anion [U(N{SiMe 3 } 2 )(CH 2 SiMe 2 N{SiMe 3 }) 2 ] − journal September 2010
Recent Advances in Organoactinide Chemistry As Exemplified by Cyclopentadienyl Compounds journal March 2013
Anionic triscyclopentadienyluranium(III) hydrides journal November 1992
Tantalum Complexes Supported by Asymmetric [ONO] Ligands. The Role of Weakly Coordinating Anions on Their Reactivity journal February 2012
Exploring the Insertion Chemistry of Tetrabenzyluranium Using Carbonyls and Organoazides journal March 2013
Organoactinide phosphine/phosphite coordination chemistry. Facile hydride-induced dealkoxylation and the formation of actinide phosphinidene complexes journal May 1984
Structural Dichotomy in Six-Coordinate d 0 Complexes:  Trigonal Prismatic ( t Bu 3 SiC⋮C) 6 Ta - and Octahedral ( t Bu 3 SiC⋮C) 6 M 2- (M = Zr, Hf) journal October 1998
Acidities of anilines in dimethyl sulfoxide solution journal April 1988
Cationic Thorium Alkyl Complexes of Rigid NON- and NNN-Donor Ligands: π-Arene Coordination as a Persistent Structural Motif journal March 2009
Thorium Oxo and Sulfido Metallocenes: Synthesis, Structure, Reactivity, and Computational Studies journal August 2011
Extremely Stable Thorium(IV) Dialkyl Complexes Supported by Rigid Tridentate 4,5-Bis(anilido)xanthene and 2,6-Bis(anilidomethyl)pyridine Ligands journal January 2007
Synthesis and Reactivity of a Silylalkyl Double Tuck-in Uranium Metallocene [(η 5 :η 1 -C 5 Me 4 SiMe 2 CH 2 ) 2 U] and its Conversion to Bis(tethered) Metallocenes journal December 2009
Small Molecule Activation Mediated by a Thorium Terminal Imido Metallocene journal July 2015
Convenient access to the anhydrous thorium tetrachloride complexes ThCl4(DME)2, ThCl4(1,4-dioxane)2 and ThCl4(THF)3.5 using commercially available and inexpensive starting materials journal January 2010
Thorium-mediated ring-opening of tetrahydrofuran and the development of a new thorium starting material: preparation and chemistry of ThI4(DME)2 journal January 2012
Chemistry of Indium(III) Tris(cyclopentadienide). Reactions with Diphenylphosphine, tert -Butyl Alcohol, and Acetylacetone. Cyclopentadiene and Reductive Elimination Reactions journal April 2003
The role of 5f-orbital participation in unexpected inversion of the σ-bond metathesis reactivity trend of triamidoamine thorium( iv ) and uranium( iv ) alkyls journal January 2014
Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions journal September 2016
Equilibrium acidities in dimethyl sulfoxide solution journal December 1988
Thorium(IV) and Uranium(IV) Ketimide Complexes Prepared by Nitrile Insertion into Actinide−Alkyl and −Aryl Bonds journal September 2004
Mono(pentamethylcyclopentadienyl)thorium Chemistry:  Synthesis, Structural Characterization, and Reactivity of Aryloxide and Alkyl Derivatives journal January 1996

Figures / Tables (15)

Fig. 1(p. 3)figure Fig. 1
Scheme 1(p. 3)figure Scheme 1
Scheme 2(p. 3)figure Scheme 2
Fig. 2(p. 4)figure Fig. 2
Fig. 3(p. 5)figure Fig. 3
Fig. 4(p. 5)figure Fig. 4
Scheme 3(p. 5)figure Scheme 3
Scheme 4(p. 6)figure Scheme 4
Scheme 5(p. 6)figure Scheme 5
Fig. 5(p. 7)figure Fig. 5
Fig. 6(p. 8)figure Fig. 6
Fig. 7(p. 8)figure Fig. 7
Scheme 6(p. 8)figure Scheme 6
Fig. 8(p. 9)figure Fig. 8
Fig. 9(p. 9)figure Fig. 9

Similar Records

Sterically demanding aryloxides as supporting ligands in organoactinide chemistry. Synthesis, structural characterization, and reactivity of Th(O-2,6-t-Bu{sub 2}C{sub 6}H{sub 3}){sub 2}(CH{sub 2}SiMe{sub 3}){sub 2} and formation of the trimeric thorium hydride Th{sub 3}H{sub 6}(O-2,6-t-Bu{sub 2}C{sub 6}H{sub 3}){sub 6}
Journal Article · Tue Feb 06 00:00:00 EST 1996 · Organometallics · OSTI ID:1421572
+1 more
Chloro-, methyl-, and (tetrahydroborato)tris((hexamethyldisilyl)amido)thorium(IV) and -uranium(IV). Crystal structure of (tetrahydroborato)tris((hexamethyldisilyl)amido)thorium(IV)
Journal Article · Tue May 01 00:00:00 EDT 1979 · Inorg. Chem.; (United States) · OSTI ID:1421572
+1 more
Amidinate Supporting Ligands Influence Molecularity in Formation of Uranium Nitrides
Journal Article · Mon Apr 12 00:00:00 EDT 2021 · Inorganic Chemistry · OSTI ID:1421572
+8 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY