Lanthanide(III) di- and tetra-nuclear complexes supported by a chelating tripodal tris(amidate) ligand
Abstract
Syntheses, structural, and spectroscopic characterization of multinuclear tris(amidate) lanthanide complexes is described. Addition of K3[N(o-PhNC(O)tBu)3] to LnX3 (LnX3 = LaBr3, CeI3, and NdCl3) in N,N-dimethylformamide (DMF) results in the generation of dinuclear complexes, [Ln(N(o-PhNC(O)tBu)3)(DMF)]2(μ-DMF) (Ln = La (1), Ce (2), Nd(3)), in good yields. Syntheses of tetranuclear complexes, [Ln(N(o-PhNC(O)tBu)3)]4 (Ln = Ce (4), Nd(5)), resulted from protonolysis of Ln[N(SiMe3)2]3 (Ln = Ce, Nd) with N(o-PhNCH(O)tBu)3. As a result, in the solid-state, complexes 1–5 exhibit coordination modes of the tripodal tris(amidate) ligand that are unique to the 4f elements and have not been previously observed in transition metal systems.
- Authors:
-
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Emory Univ., Atlanta, GA (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1239314
- Report Number(s):
- LA-UR-15-20407
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- AC52-06NA25396
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 54; Journal Issue: 8; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Brown, Jessie L., Jones, Matthew B., Gaunt, Andrew J., Scott, Brian L., MacBeth, Cora E., and Gordon, John C. Lanthanide(III) di- and tetra-nuclear complexes supported by a chelating tripodal tris(amidate) ligand. United States: N. p., 2015.
Web. doi:10.1021/acs.inorgchem.5b00299.
Brown, Jessie L., Jones, Matthew B., Gaunt, Andrew J., Scott, Brian L., MacBeth, Cora E., & Gordon, John C. Lanthanide(III) di- and tetra-nuclear complexes supported by a chelating tripodal tris(amidate) ligand. United States. https://doi.org/10.1021/acs.inorgchem.5b00299
Brown, Jessie L., Jones, Matthew B., Gaunt, Andrew J., Scott, Brian L., MacBeth, Cora E., and Gordon, John C. Mon .
"Lanthanide(III) di- and tetra-nuclear complexes supported by a chelating tripodal tris(amidate) ligand". United States. https://doi.org/10.1021/acs.inorgchem.5b00299. https://www.osti.gov/servlets/purl/1239314.
@article{osti_1239314,
title = {Lanthanide(III) di- and tetra-nuclear complexes supported by a chelating tripodal tris(amidate) ligand},
author = {Brown, Jessie L. and Jones, Matthew B. and Gaunt, Andrew J. and Scott, Brian L. and MacBeth, Cora E. and Gordon, John C.},
abstractNote = {Syntheses, structural, and spectroscopic characterization of multinuclear tris(amidate) lanthanide complexes is described. Addition of K3[N(o-PhNC(O)tBu)3] to LnX3 (LnX3 = LaBr3, CeI3, and NdCl3) in N,N-dimethylformamide (DMF) results in the generation of dinuclear complexes, [Ln(N(o-PhNC(O)tBu)3)(DMF)]2(μ-DMF) (Ln = La (1), Ce (2), Nd(3)), in good yields. Syntheses of tetranuclear complexes, [Ln(N(o-PhNC(O)tBu)3)]4 (Ln = Ce (4), Nd(5)), resulted from protonolysis of Ln[N(SiMe3)2]3 (Ln = Ce, Nd) with N(o-PhNCH(O)tBu)3. As a result, in the solid-state, complexes 1–5 exhibit coordination modes of the tripodal tris(amidate) ligand that are unique to the 4f elements and have not been previously observed in transition metal systems.},
doi = {10.1021/acs.inorgchem.5b00299},
journal = {Inorganic Chemistry},
number = 8,
volume = 54,
place = {United States},
year = {Mon Apr 06 00:00:00 EDT 2015},
month = {Mon Apr 06 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Dissociation of Diglycolamide Complexes of Ln 3+ (Ln = La–Lu) and An 3+ (An = Pu, Am, Cm): Redox Chemistry of 4f and 5f Elements in the Gas Phase Parallels Solution Behavior
journal, October 2014
- Gong, Yu; Tian, Guoxin; Rao, Linfeng
- Inorganic Chemistry, Vol. 53, Issue 22
Covalency in the f-element–chalcogen bond
journal, October 2007
- Ingram, Kieran I. M.; Kaltsoyannis, Nikolas; Gaunt, Andrew J.
- Journal of Alloys and Compounds, Vol. 444-445
The remarkable efficiency of N-heterocyclic carbenes in lanthanide(iii)/actinide(iii) differentiation
journal, January 2005
- Mehdoui, Thouraya; Berthet, Jean-Claude; Thuéry, Pierre
- Chemical Communications, Issue 22
Structural and electrochemical characterization of a cerium( iv ) hydroxamate complex: implications for the beneficiation of light rare earth ores
journal, January 2014
- Lee, Heui Beom; Bogart, Justin A.; Carroll, Patrick J.
- Chem. Commun., Vol. 50, Issue 40
A review of the beneficiation of rare earth element bearing minerals
journal, February 2013
- Jordens, Adam; Cheng, Ying Ping; Waters, Kristian E.
- Minerals Engineering, Vol. 41
Coordination of Lanthanide Triflates and Perchlorates with N , N , N ‘, N ‘-Tetramethylsuccinamide
journal, October 2000
- Rapko, Brian M.; McNamara, Bruce K.; Rogers, Robin D.
- Inorganic Chemistry, Vol. 39, Issue 21
Experimental and Theoretical Comparison of Actinide and Lanthanide Bonding in M[N(EPR 2 ) 2 ] 3 Complexes (M = U, Pu, La, Ce; E = S, Se, Te; R = Ph, i Pr, H)
journal, January 2008
- Gaunt, Andrew J.; Reilly, Sean D.; Enriquez, Alejandro E.
- Inorganic Chemistry, Vol. 47, Issue 1
Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2013
journal, February 2015
- Edelmann, Frank T.
- Coordination Chemistry Reviews, Vol. 284
Review: Lanthanide coordination chemistry: from old concepts to coordination polymers
journal, September 2014
- Bünzli, Jean-Claude G.
- Journal of Coordination Chemistry, Vol. 67, Issue 23-24
Synthesis and Characterization of Nitrogen-Rich Macrocyclic Ligands and an Investigation of Their Coordination Chemistry with Lanthanum(III)
journal, December 2014
- Wilson, Justin J.; Birnbaum, Eva R.; Batista, Enrique R.
- Inorganic Chemistry, Vol. 54, Issue 1
Lower Denticity Leading to Higher Stability: Structural and Solution Studies of Ln(III)–OBETA Complexes
journal, November 2014
- Negri, Roberto; Baranyai, Zsolt; Tei, Lorenzo
- Inorganic Chemistry, Vol. 53, Issue 23
Lanthanide Complexes Coordinated by a Dianionic Bis(amidinate) Ligand with a Rigid Naphthalene Linker
journal, June 2010
- Yakovenko, Marina V.; Cherkasov, Anton V.; Fukin, Georgy K.
- European Journal of Inorganic Chemistry, Vol. 2010, Issue 21
Differences in actinide metal–ligand orbital interactions: comparison of U(iv) and Pu(iv) β-ketoiminate N,O donor complexes
journal, January 2011
- Schnaars, David D.; Batista, Enrique R.; Gaunt, Andrew J.
- Chemical Communications, Vol. 47, Issue 27
Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An IV ( Ar acnac) 4 Complexes (An = Th, U, Np, Pu; Ar acnac = Ar N C(Ph)CHC(Ph) O ; Ar = 3,5- t Bu 2 C 6 H 3 )
journal, July 2012
- Schnaars, David D.; Gaunt, Andrew J.; Hayton, Trevor W.
- Inorganic Chemistry, Vol. 51, Issue 15
Excellent Selectivity for Actinides with a Tetradentate 2,9-Diamide-1,10-Phenanthroline Ligand in Highly Acidic Solution: A Hard–Soft Donor Combined Strategy
journal, January 2014
- Xiao, Cheng-Liang; Wang, Cong-Zhi; Yuan, Li-Yong
- Inorganic Chemistry, Vol. 53, Issue 3
Complexation of Lanthanides(III), Americium(III), and Uranium(VI) with Bitopic N,O Ligands: an Experimental and Theoretical Study
journal, July 2011
- Marie, Cécile; Miguirditchian, Manuel; Guillaumont, Dominique
- Inorganic Chemistry, Vol. 50, Issue 14
New Bitopic Ligands for the Group Actinide Separation by Solvent Extraction
journal, March 2011
- Marie, Cécile; Miguirditchian, Manuel; Guillaneux, Denis
- Solvent Extraction and Ion Exchange, Vol. 29, Issue 2
Rare-Earth Amidate Complexes. Easily Accessed Initiators For ε-Caprolactone Ring-Opening Polymerization
journal, August 2008
- Stanlake, Louisa J. E.; Beard, J. David; Schafer, Laurel L.
- Inorganic Chemistry, Vol. 47, Issue 18
Synthesis and structural diversity of lanthanide amidate complexes and their catalytic activities for the ring-opening polymerization of rac-lactide
journal, May 2013
- Hu, Xiaolin; Lu, Chengrong; Wu, Bing
- Journal of Organometallic Chemistry, Vol. 732
Synthesis and Reactivities of Guanidinate Dianion Complexes of Heterobimetallic Lanthanide−Lithium Cp 2 Ln[(CyN) 2 CNPh]Li(THF) 3
journal, March 2010
- Zheng, Pengzhi; Hong, Jianquan; Liu, Ruiting
- Organometallics, Vol. 29, Issue 5
Reactivity of Organolanthanide and Organolithium Complexes Containing the Guanidinate Ligands toward Isocyanate or Carbodiimide: Synthesis and Crystal Structures
journal, February 2005
- Zhang, Jie; Zhou, Xigeng; Cai, Ruifang
- Inorganic Chemistry, Vol. 44, Issue 3
Yttrium (amidate) complexes for catalytic C–N bond formation. Rapid, room temperature amidation of aldehydes
journal, January 2012
- Thomson, Jaclyn A.; Schafer, Laurel L.
- Dalton Transactions, Vol. 41, Issue 26
Synthesis, structure, and catalytic activity of organoyttrium complexes with chiral binaphthyl-based amidate ligands
journal, January 2011
- Zhang, Furen; Zhang, Jiaxin; Song, Haibin
- Inorganic Chemistry Communications, Vol. 14, Issue 1
Synthesis, structure, and catalytic activity of organolanthanides with chiral biphenyl-based tridentate amidate ligands
journal, May 2011
- Wang, Qiuwen; Zhang, Furen; Song, Haibin
- Journal of Organometallic Chemistry, Vol. 696, Issue 10
Organolanthanide-Based Coordination and Insertion Reactivity of the Anion Formed by Deprotonation of ε-Caprolactam
journal, October 2001
- Evans, William J.; Fujimoto, Cy H.; Ziller, Joseph W.
- Organometallics, Vol. 20, Issue 22
Syntheses of {(MeC5H4)2Ln[OC̄H2]}2 (Ln=Yb, Y, Er) and the X-ray crystal structure of the ytterbium complex
journal, April 2001
- Wang, Yaorong; Shen, Qi; Wu, Liping
- Journal of Organometallic Chemistry, Vol. 626, Issue 1-2
Bis- and Mono(amidate) Complexes of Yttrium: Synthesis, Characterization, and Use as Precatalysts for the Hydroamination of Aminoalkenes
journal, June 2009
- Stanlake, Louisa J. E.; Schafer, Laurel L.
- Organometallics, Vol. 28, Issue 14
Insertion Reaction of Phenyl Isocyanate into the Ln−C σ-Bond of Organolanthanide Complexes: Synthesis, Characterization, and Crystal Structures of {(C 5 H 4 CH 3 ) 2 Ln[μ-η 1 :η 3 -OC(R)NPh]} 2 (Ln = Sm, Dy, Er, Ho; R = n -butyl, α-naphthyl)
journal, December 2001
- Zhou, Xi-geng; Zhang, Li-bei; Zhu, Ming
- Organometallics, Vol. 20, Issue 26
Insertion Reactions of PhEtCCO and PhNCO into Ln-S (Ln = Er, Y, Yb) Bond of [Cp2Ln(μ-SEt)]2
journal, February 2006
- Zhang, Chunmei; Lin, Yanghui; Chen, Zhenxia
- Journal of Rare Earths, Vol. 24, Issue 1
Synthetic, spectral and structural studies of mononuclear tris(κ2-amidate) aluminium complexes supported by tripodal ligands
journal, January 2010
- Jones, Matthew B.; Hardcastle, Kenneth I.; MacBeth, Cora E.
- Polyhedron, Vol. 29, Issue 1
Chelating tris(amidate) ligands: versatile scaffolds for nickel(ii)
journal, January 2010
- Jones, Matthew B.; Newell, Brian S.; Hoffert, Wesley A.
- Dalton Trans., Vol. 39, Issue 2
Oxygen Activation and Intramolecular C–H Bond Activation by an Amidate-Bridged Diiron(II) Complex
journal, July 2011
- Jones, Matthew B.; Hardcastle, Kenneth I.; Hagen, Karl S.
- Inorganic Chemistry, Vol. 50, Issue 14
Tripodal Phenylamine-Based Ligands and Their Co II Complexes
journal, October 2007
- Jones, Matthew B.; MacBeth, Cora E.
- Inorganic Chemistry, Vol. 46, Issue 20
Synthesis, Characterization, and Reactivity of Iron Trisamidoamine Complexes That Undergo Both Metal- and Ligand-Centered Oxidative Transformations
journal, January 2008
- Çelenligil-Çetin, Remle; Paraskevopoulou, Patrina; Dinda, Rupam
- Inorganic Chemistry, Vol. 47, Issue 3
Crystal and molecular structure of the decacoordinate compound ((hydroxyethyl)ethylenediaminetriacetato)diaquolanthanum(III) trihydrate
journal, August 1978
- Fuller, Charles C.; Molzahn, David K.; Jacobson, Robert A.
- Inorganic Chemistry, Vol. 17, Issue 8
Structural Studies of Rare Earth/Transition Metal Complex Ion Systems as a Basis for Understanding Their Thermal Decomposition to Mixed Oxides
journal, March 2005
- Brayshaw, Philippa A.; Hall, Annegret K.; Harrison, William T. A.
- European Journal of Inorganic Chemistry, Vol. 2005, Issue 6
First characterization of an uranium(III) complex with a carbonyl-containing ligand: Syntheses and X-ray crystal structures of the homoleptic dimethylformamide complexes [M(dmf)n]I3 (M=Ce, Nd and n=8; M=La, Ce, U and n=9)
journal, May 2006
- Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel
- Polyhedron, Vol. 25, Issue 7
A series of three-dimensional lanthanide(iii) coordination polymers of 2,5-dihydroxy-1,4-benzenedicarboxylic acid based on dinuclear lanthanide units
journal, January 2011
- Wang, Yu-Ling; Jiang, Yun-Liang; Liu, Qing-Yan
- CrystEngComm, Vol. 13, Issue 15
Reduction of structural dimensionality through incorporation of auxiliary ligands in lanthanide tetracyanoplatinates
journal, May 2011
- Stojanovic, Milorad; Robinson, Nicholas J.; Chen, Xi
- Inorganica Chimica Acta, Vol. 370, Issue 1
Structural and Density Functional Studies of Uranium(III) and Lanthanum(III) Complexes with a Neutral Tripodal N-Donor Ligand Suggesting the Presence of a U−N Back-Bonding Interaction
journal, May 2002
- Mazzanti, Marinella; Wietzke, Raphaël; Pécaut, Jacques
- Inorganic Chemistry, Vol. 41, Issue 9
A rare uranium(III) complex of a tripodal aromatic amine and its lanthanum analogue
journal, January 1998
- Wietzke, Raphaël; Mazzanti, Marinella; Latour, Jean-Marc
- Journal of the Chemical Society, Dalton Transactions, Issue 24
X-ray and Multinuclear Magnetic Resonance Study of the Complexes of Lanthanum(III) with 2,2':6',2''-Terpyridine
journal, June 1995
- Frechette, Monique; Bensimon, Corinne
- Inorganic Chemistry, Vol. 34, Issue 13
Lanthanide(III) Complexes of 4,10-Bis(phosphonomethyl)-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (trans-H6do2a2p) in Solution and in the Solid State: Structural Studies Along the Series
journal, June 2010
- Campello, M. Paula C.; Lacerda, Sara; Santos, Isabel C.
- Chemistry - A European Journal, Vol. 16, Issue 28
Cerium(IV) alkoxides with functional alcohols: Synthesis and molecular structure of Ce2(OiPr)6(μ-OC2H4NMeC2H4NMe2)2
journal, January 1992
- Hubert-Pfalzgraf, Liliane G.; El Khokh, Norddine; Daran, Jean-Claude
- Polyhedron, Vol. 11, Issue 1
Three novel lanthanide complexes with imidazole-4,5-dicarboxylate ligand: Hydrothermal syntheses, structural characterization, and properties
journal, January 2010
- Li, Zhao-Yang; Zhang, Zhi-Min; Dai, Jing-Wei
- Journal of Molecular Structure, Vol. 963, Issue 1
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
Magnetic Properties versus Network Dimensionality of Cerium(III) Octacyanotungstate(V) Compounds
journal, April 2010
- Kozieł, Marcin; Pełka, Robert; Rams, Michał
- Inorganic Chemistry, Vol. 49, Issue 9
Lanthanide Coordination Polymers with Tetrafluoroterephthalate as a Bridging Ligand: Thermal and Optical Properties
journal, March 2012
- Seidel, Christiane; Lorbeer, Chantal; Cybińska, Joanna
- Inorganic Chemistry, Vol. 51, Issue 8
A molecular precursor approach to monodisperse scintillating CeF3 nanocrystals
journal, January 2013
- Mishra, Shashank; Jeanneau, Erwann; Bulin, Anne-Laure
- Dalton Transactions, Vol. 42, Issue 35
A tetranuclear neodymium cage which tightly binds sodium carbonate
molecules
journal, January 1997
- B. Deacon, Glen; Feng, Tiecheng; C. R. Hockless, David
- Chemical Communications, Issue 4
Selective formation of lanthanide(III) complexes with polyaminopolycarboxylate: Unprecedented tetranuclear neodymium(III) complex containing alkoxo and carboxylato bridges
journal, September 2005
- Miyashita, Yoshitaro; Sanada, Masateru; Islam, Md. Monirul
- Inorganic Chemistry Communications, Vol. 8, Issue 9
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist
journal, May 2010
- Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H.
- Organometallics, Vol. 29, Issue 9
Facile synthesis, characterization, and evaluation of neurotoxicity effect of cerium oxide nanoparticles
journal, August 2013
- Darroudi, Majid; Hakimi, Mohammad; Sarani, Mina
- Ceramics International, Vol. 39, Issue 6
Luminescence, absorption, and Stern–Volmer studies of cerium chloride and nitrate compounds in acidic and neutral aqueous, and non-aqueous solutions
journal, February 2013
- Forcha, Derick; Brown, Kwame J.; Assefa, Zerihun
- Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 103
Energy transfer and photoextinction from Ln3+ to Tb3+ and Eu3+ in aqueous chloride solutions
journal, November 2008
- Wang, Jiwei; Tanner, Peter A.
- Journal of Luminescence, Vol. 128, Issue 11
Molecular Dynamics Studies of Concentrated Binary Aqueous Solutions of Lanthanide Salts: Structures and Exchange Dynamics
journal, January 2010
- Duvail, Magali; Ruas, Alexandre; Venault, Laurent
- Inorganic Chemistry, Vol. 49, Issue 2
A new simple criterion for distinguishing the types of structures in eight-coordinate complexes: The pattern of bond angles
journal, September 1995
- Haigh, C. W.
- Polyhedron, Vol. 14, Issue 20-21
Bis({tris[2-(3,5-di- tert -butyl-2-oxidobenzylideneamino)ethyl]amine}cerium(III)) diethyl ether solvate
journal, October 2010
- Dröse, Peter; Hrib, Cristian G.; Edelmann, Frank T.
- Acta Crystallographica Section E Structure Reports Online, Vol. 66, Issue 11
Solvent Exchange and Electron-Spin Relaxation on Homoleptic Acetonitrile Complexes of Trivalent Lanthanides
journal, January 2015
- Bodizs, Gabriella; Helm, Lothar
- Inorganic Chemistry, Vol. 54, Issue 4
Luminescence study on preferential solvation of Europium(III) in water/non-aqueous solvent mixtures
journal, July 2001
- Kimura, Takaumi; Nagaishi, Ryuji; Kato, Yoshiharu
- Journal of Alloys and Compounds, Vol. 323-324
Low co-ordination numbers in lanthanide and actinide compounds. Part I. The preparation and characterization of tris{bis(trimethylsilyl)-amido}lanthanides
journal, January 1973
- Bradley, Donald C.; Ghotra, Joginder S.; Hart, F. Alan
- Journal of the Chemical Society, Dalton Transactions, Issue 10
Amine Elimination Reactions between Homoleptic Silylamide Lanthanide Complexes and an Isopropylidene-Bridged Cyclopentadiene−Fluorene System
journal, June 2002
- Dash, Aswini K.; Razavi, Abbas; Mortreux, André
- Organometallics, Vol. 21, Issue 15
Synthesis and Characterization of Volatile, Fluorine-Free β-Ketoiminate Lanthanide MOCVD Precursors and Their Implementation in Low-Temperature Growth of Epitaxial CeO 2 Buffer Layers for Superconducting Electronics
journal, October 2002
- Edleman, Nikki L.; Wang, Anchuan; Belot, John A.
- Inorganic Chemistry, Vol. 41, Issue 20
Cerium( iii ) dialkyl dithiocarbamates from [Ce{N(SiMe 3 ) 2 } 3 ] and tetraalkylthiuram disulfides, and [Ce(κ 2 -S 2 CNEt 2 ) 4 ] from the Ce III precursor; Tb III and Nd III analogues
journal, January 2004
- Hitchcock, Peter B.; Hulkes, Alexander G.; Lappert, Michael F.
- Dalton Trans., Issue 1
Single-crystal structure validation with the program PLATON
journal, January 2003
- Spek, A. L.
- Journal of Applied Crystallography, Vol. 36, Issue 1, p. 7-13
Works referencing / citing this record:
Synthesis and characterization of bridged bis(amidato) rare earth metal amides and their applications in C–N bond formation reactions
journal, January 2016
- Zhao, Bei; Xiao, Yang; Yuan, Dan
- Dalton Transactions, Vol. 45, Issue 9
Synthesis and Characterization of Amidato Divalent Lanthanide Complexes and Their Use in Forming 2,4-Quinazolidinones from CO 2 and 2-Aminobenzonitriles
journal, April 2016
- Wang, Qianyu; Lu, Chengrong; Zhao, Bei
- European Journal of Organic Chemistry, Vol. 2016, Issue 14