Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Piano-stool lutetium amido and imido compounds supported by a constrained bis(oxazoline)cyclopentadienyl ligand

Journal Article · · Inorganic Chemistry
 [1];  [1];  [1];  [1];  [1];  [1]
  1. Iowa State Univ., Ames, IA (United States)
+ Show Author Affiliations
{BoMCptet}Lu(CH2Ph)2 (1; BoMCptet = MeC(OxMe2 2C5Me4; OxMe2 = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of BoMCptetH and Lu(CH2Ph)3THF3. Compound 1 reacts with 1 or 2 equiv of H2NCH2R (R = C6H5, 1-C10H7) to give the corresponding imido complexes [{BoMCptet}LuNCH2R]2 (R = C6H5 (2a), 1-C10H7 (2b)) or amido complexes {BoMCptet}Lu(NHCH2R)2 (R = C6H5 (3a), 1-C10H7 (3b)). When isolated, the imido species are insoluble in nonprotic organic solvents. Crystallographic characterization reveals dimeric [{BoMCptet}LuNCH2(1-C10H7)]2 in the solid state. The reaction of 1 and NH3B(C6F5)3 affords crystallographically characterized {BoMCptet}Lu{NHB(C6F5)2}C6F5. This species is proposed to form via a transient lutetium imido, which undergoes C6F5 migration to the lutetium center.
Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27)
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1221929
Report Number(s):
IS-J--8759
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 14 Vol. 54; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (66)

The Search for New-Generation Olefin Polymerization Catalysts: Life beyond Metallocenes journal February 1999
Intermolecular Hydroamination of Alkynes Catalyzed by Dimethyltitanocene journal November 1999
The Mechanism of the [Cp2TiMe2]-Catalyzed Intermolecular Hydroamination of Alkynes journal June 2001
The Mechanism of Hydroamination of Allenes, Alkynes, and Alkenes Catalyzed by Cyclopentadienyltitanium-Imido Complexes: A Density Functional Study journal December 2001
Lanthanide-Imido Complexes and Their Reactions with Benzonitrile journal January 2005
Kinetic Control and Multiple Mechanisms for CH Bond Activation by a ZrN Complex journal July 2007
Evidence for the Existence of a Terminal Imidoscandium Compound: Intermolecular CH Activation and Complexation Reactions with the Transient ScNAr Species journal October 2008
A Highly Enantioselective Zirconium Catalyst for Intramolecular Alkene Hydroamination: Significant Isotope Effects on Rate and Stereoselectivity journal January 2011
Reactivity of a Scandium Terminal Imido Complex Towards Unsaturated Substrates journal June 2011
Synthesis and Structures of the First Cationic Perfluoroaryllanthanoid(II) Complexes journal April 2004
An Easy-To-Use, Regioselective, and Robust Bis(amidate) Titanium Hydroamination Precatalyst: Mechanistic and Synthetic Investigations toward the Preparation of Tetrahydroisoquinolines and Benzoquinolizine Alkaloids journal February 2007
Mechanism of the Intramolecular Hydroamination of Alkenes Catalyzed by Neutral Indenyltitanium Complexes: A DFT Study journal November 2008
Rare-Earth-Metal Methyl, Amide, and Imide Complexes Supported by a Superbulky Scorpionate Ligand journal November 2014
Rare-Earth Metal Complexes with Terminal Imido Ligands: Rare-Earth Metal Complexes with Terminal Imido Ligands journal February 2015
Living ring-opening metathesis polymerization catalyzed by well-characterized transition-metal alkylidene complexes journal May 1990
Reactions and Applications of Titanium Imido Complexes journal November 2005
Methane vs benzene activation via transient tantalum amido-imido complex tert-Bu3SiNHTa(:NSiBu3-tert)2: structure of (py)2MeTa(:NSiBu3-tert)2 journal January 1993
Intra- and Intermolecular N−H···F−C Hydrogen-Bonding Interactions in Amine Adducts of Tris(pentafluorophenyl)borane and -alane journal August 2005
Stabilization of Unsolvated Europium and Ytterbium Pentafluorophenyls by π-Bonding Encapsulation through a Sterically Crowded Triazenido Ligand journal October 2005
New Syntheses and Structural Characterization of NH 3 BH 2 Cl and (BH 2 NH 2 ) 3 and Thermal Decomposition Behavior of NH 3 BH 2 Cl journal November 2012
Bridging alkylimido complexes of the Group 4B transition metals journal July 1979
Organolanthanide-catalyzed hydroamination. A kinetic, mechanistic, and diastereoselectivity study of the cyclization of N-unprotected amino olefins journal January 1992
Stoichiometric and catalytic hydroamination of alkynes and allene by zirconium bisamides Cp2Zr(NHR)2 journal February 1992
Zirconium-Mediated Imine Metathesis. Synthesis of 2,4-Diaza-1-zirconiacyclobutanes and the Mechanism of Their Reactions with Imines and Alkynes journal March 1994
Generation, alkyne cycloaddition, arene carbon-hydrogen activation, nitrogen-hydrogen activation and dative ligand trapping reactions of the first monomeric imidozirconocene (Cp2Zr:NR) complexes journal December 1988
Methane and benzene activation via transient (tert-Bu3SiNH)2Zr:NSi-tert-Bu3 journal December 1988
.sigma.-Bond metathesis for carbon-hydrogen bonds of hydrocarbons and Sc-R (R = H, alkyl, aryl) bonds of permethylscandocene derivatives. Evidence for noninvolvement of the .pi. system in electrophilic activation of aromatic and vinylic C-H bonds journal January 1987
Imidotitanium Complexes as Hydroamination Catalysts:  Substantially Enhanced Reactivity from an Unexpected Cyclopentadienide/Amide Ligand Exchange journal March 2001
Mechanistic Aspects of Samarium-Mediated σ-Bond Activations of Arene C−H and Arylsilane Si−C Bonds journal October 2001
Use of Group 4 Bis(sulfonamido) Complexes in the Intramolecular Hydroamination of Alkynes and Allenes journal September 2003
C 2 -Symmetric Bis(oxazolinato)lanthanide Catalysts for Enantioselective Intramolecular Hydroamination/Cyclization journal December 2003
Titanium Hydrazido and Imido Complexes:  Synthesis, Structure, Reactivity, and Relevance to Alkyne Hydroamination journal February 2004
C−H Bond Activation of Hydrocarbons by an Imidozirconocene Complex journal January 2004
Tetranuclear Rare Earth Metal Polyhydrido Complexes Composed of “(C 5 Me 4 SiMe 3 )LnH 2 ” Units. Unique Reactivities toward Unsaturated C−C, C−N, and C−O Bonds journal February 2004
Hydrogen for Fluorine Exchange in C 6 F 6 and C 6 F 5 H by Monomeric [1,3,4-(Me 3 C) 3 C 5 H 2 ] 2 CeH:  Experimental and Computational Studies journal January 2005
Mechanism of Catalytic Cyclohydroamination by Zirconium Salicyloxazoline Complexes journal November 2010
Carbon–Silicon and Carbon–Carbon Bond Formation by Elimination Reactions at Metal N-Heterocyclic Carbene Complexes journal August 2011
Evidence for the Existence of Terminal Scandium Imidos: Mechanistic Studies Involving Imido–Scandium Bond Formation and C–H Activation Reactions journal November 2012
Highly Enantioselective Zirconium-Catalyzed Cyclization of Aminoalkenes journal April 2013
Hydrocarbon Activation via Reversible 1,2-RH-Elimination from ( t Bu 3 SiNH) 3 ZrR:  Synthetic, Structural, and Mechanistic Investigations
  • Schaller, Christopher P.; Cummins, Christopher C.; Wolczanski, Peter T.
  • Journal of the American Chemical Society, Vol. 118, Issue 3 https://doi.org/10.1021/ja950745i
journal January 1996
Reactivity of a Terminal Ti(IV) Imido Complex toward Alkenes and Alkynes:  Cycloaddition vs C−H Activation journal December 1998
Study of the N−H···H−B Dihydrogen Bond Including the Crystal Structure of BH 3 NH 3 by Neutron Diffraction journal July 1999
Zirconium-Mediated Metathesis of Imines:  A Study of the Scope, Longevity, and Mechanism of a Complicated Catalytic System journal February 2000
[H 2 N{B(C 6 F 5 ) 3 } 2 ] - :  A New, Remarkably Stable Diborate Anion for Metallocene Polymerization Catalysts journal February 2002
A Half-Sandwich Perfluoroorganoytterbium(II) Complex from a Simple Redox Transmetalation/Ligand Exchange Synthesis journal March 2003
A New Chelating Anilido-Imine Donor Related to β-Diketiminato Ligands for Stabilization of Organoyttrium Cations journal April 2003
(Cyclopentadienylamine)scandium(2,3-dimethyl-1,3-butadiene):  A 1,3-Diene Complex of Scandium with Sc(I)- and Sc(III)-like Reactivity journal October 2003
Hydroamination of Alkynes Catalyzed by Imido Complexes of Titanium and Vanadium journal April 2004
Synthesis and Characterization of (Mono)pentamethylcyclopentadienyl Lutetium Complexes:  Formation of Bipyridyl-Stabilized Alkyls, Anilides, and Terminal Acetylides journal June 2004
Synthesis, Structure, and Ion Pair Dynamics of β-Diketiminato-Supported Organoscandium Contact Ion Pairs journal February 2005
Synthesis and Reactivity of a Terminal Scandium Imido Complex journal November 2012
σ-Bond Metathesis: A 30-Year Retrospective journal September 2013
C 3 -Symmetric Chiral Organolanthanide Complexes:  Synthesis, Characterization, and Stereospecific Polymerization of α-Olefins journal August 2007
Lutetium Alkyls Supported by a Dearomatized and Functionalized Terpyridine Ligand: Preparation of Fluorinated Anilide Complexes journal January 2008
Synthesis and Structures of Scandium and Lutetium Benzyl Complexes journal March 2008
C–H activation of a 2,2′-bipyridine ligand within (mono)pentamethylcyclopentadienyl lutetium complexes journal January 2004
New titanium and zirconium complexes with M–NH 2 bonds formed by facile deprotonation of H 3 N·B(C 6 F 5 ) 3 journal January 2005
A zwitterionic zirconium complex that catalyzes hydroamination of aminoalkenes at room temperature journal January 2010
C–H bond activation and C–N coupling reactions of methylacetylenes and allenes with an imidotitanium complex journal January 1998
Titanium dipyrrolylmethane derivatives: rapid intermolecular alkyne hydroamination journal February 2003
Amidate complexes of titanium and zirconium: a new class of tunable precatalysts for the hydroamination of alkynesElectronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/cc/b3/b304176j/ journal January 2003
Zirconium catalysed enantioselective hydroamination/cyclisationElectronic Supplementary Information (ESI) available: experimental details and characterising data for complexes and substrates, catalytic protocol, determination of ee, crystal data for [ZrL2Cl2]. See http://www.rsc.org/suppdata/cc/b4/b401493f/ journal January 2004
Lanthanide alkylidene and imido complexes journal January 2004
Syntheses and structures of mononuclear lutetium imido complexes with very short Lu–N bonds journal January 2007
Titanium hydroamination catalysts bearing a 2-aminopyrrolinato spectator ligand: monitoring the individual reaction steps journal January 2009
A scandium terminal imido complex: synthesis, structure and DFT studies journal January 2010

Cited By (2)

Organoamido zirconium( iv ) and titanium( iv ) complexes and their catalysis towards ethylene polymerization journal January 2015
Rare-earth metal and actinide organoimide chemistry journal January 2019

Figures / Tables (5)

Table 1(p. 5)table Table 1
Figure 1(p. 7)figure Figure 1
Figure 2(p. 10)figure Figure 2
Figure 3(p. 15)figure Figure 3
Scheme 1(p. 20)figure Scheme 1

Similar Records

Related Subjects

59 BASIC BIOLOGICAL SCIENCES