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

Title: 1,2-Addition and cycloaddition reactions of niobium bis(imido) and oxo imido complexes

Abstract

The bis(imido) complexes (BDI)Nb(NtBu)2 and (BDI)Nb(NtBu)(NAr) (BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate; Ar = 2,6-diisopropylphenyl) were shown to engage in 1,2-addition and [2 + 2] cycloaddition reactions with a wide variety of substrates. Reaction of the bis(imido) complexes with dihydrogen, silanes, and boranes yielded hydrido-amido-imido complexes via 1,2-addition across Nb-imido π-bonds; some of these complexes were shown to further react via insertion of carbon dioxide to give formate-amido-imido products. Similarly, reaction of (BDI)Nb(NtBu)2 with tert-butylacetylene yielded an acetylide-amido-imido complex. In contrast to these results, many related mono(imido) Nb BDI complexes do not exhibit 1,2-addition reactivity, suggesting that π-loading plays an important role in activating the Nb–N π-bonds toward addition. The same bis(imido) complexes were also shown to engage in [2 + 2] cycloaddition reactions with oxygen- and sulfur-containing heteroallenes to give carbamate- and thiocarbamate-imido complexes: some of these complexes readily dimerized to give bis-μ-sulfido, bis-μ-iminodicarboxylate, and bis-μ-carbonate complexes. The mononuclear carbamate imido complex (BDI)Nb(NAr)(N(tBu)CO2) (12) could be induced to eject tert-butylisocyanate to generate a four-coordinate terminal oxo imido intermediate, which could be trapped as the five-coordinate pyridine or DMAP adduct. The DMAP adducted oxo imido complex (BDI)NbO(NAr)(DMAP) (16) was shown to engage in 1,2-addition of silanes across the Nb-oxo π-bond; this represents amore » new reaction pathway in group 5 chemistry.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]
  1. Department of Chemistry, University of California, Berkeley, USA
  2. Department of Chemistry, University of California, Berkeley, USA, Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR); National Institutes of Health (NIH)
OSTI Identifier:
1671349
Alternate Identifier(s):
OSTI ID: 1763681
Grant/Contract Number:  
AC02-05CH11231; CHE-1465188; 1954612; FA9550-11-1-0008; DGE 1752814; S10-RR027172
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 42; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Fostvedt, Jade I., Grant, Lauren N., Kriegel, Benjamin M., Obenhuber, Andreas H., Lohrey, Trevor D., Bergman, Robert G., and Arnold, John. 1,2-Addition and cycloaddition reactions of niobium bis(imido) and oxo imido complexes. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/D0SC03489D.
Fostvedt, Jade I., Grant, Lauren N., Kriegel, Benjamin M., Obenhuber, Andreas H., Lohrey, Trevor D., Bergman, Robert G., & Arnold, John. 1,2-Addition and cycloaddition reactions of niobium bis(imido) and oxo imido complexes. United Kingdom. https://doi.org/10.1039/D0SC03489D
Fostvedt, Jade I., Grant, Lauren N., Kriegel, Benjamin M., Obenhuber, Andreas H., Lohrey, Trevor D., Bergman, Robert G., and Arnold, John. Wed . "1,2-Addition and cycloaddition reactions of niobium bis(imido) and oxo imido complexes". United Kingdom. https://doi.org/10.1039/D0SC03489D.
@article{osti_1671349,
title = {1,2-Addition and cycloaddition reactions of niobium bis(imido) and oxo imido complexes},
author = {Fostvedt, Jade I. and Grant, Lauren N. and Kriegel, Benjamin M. and Obenhuber, Andreas H. and Lohrey, Trevor D. and Bergman, Robert G. and Arnold, John},
abstractNote = {The bis(imido) complexes (BDI)Nb(NtBu)2 and (BDI)Nb(NtBu)(NAr) (BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate; Ar = 2,6-diisopropylphenyl) were shown to engage in 1,2-addition and [2 + 2] cycloaddition reactions with a wide variety of substrates. Reaction of the bis(imido) complexes with dihydrogen, silanes, and boranes yielded hydrido-amido-imido complexes via 1,2-addition across Nb-imido π-bonds; some of these complexes were shown to further react via insertion of carbon dioxide to give formate-amido-imido products. Similarly, reaction of (BDI)Nb(NtBu)2 with tert-butylacetylene yielded an acetylide-amido-imido complex. In contrast to these results, many related mono(imido) Nb BDI complexes do not exhibit 1,2-addition reactivity, suggesting that π-loading plays an important role in activating the Nb–N π-bonds toward addition. The same bis(imido) complexes were also shown to engage in [2 + 2] cycloaddition reactions with oxygen- and sulfur-containing heteroallenes to give carbamate- and thiocarbamate-imido complexes: some of these complexes readily dimerized to give bis-μ-sulfido, bis-μ-iminodicarboxylate, and bis-μ-carbonate complexes. The mononuclear carbamate imido complex (BDI)Nb(NAr)(N(tBu)CO2) (12) could be induced to eject tert-butylisocyanate to generate a four-coordinate terminal oxo imido intermediate, which could be trapped as the five-coordinate pyridine or DMAP adduct. The DMAP adducted oxo imido complex (BDI)NbO(NAr)(DMAP) (16) was shown to engage in 1,2-addition of silanes across the Nb-oxo π-bond; this represents a new reaction pathway in group 5 chemistry.},
doi = {10.1039/D0SC03489D},
journal = {Chemical Science},
number = 42,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/D0SC03489D

Save / Share:

Works referenced in this record:

Catalytic Hydroamination of Alkynes and Norbornene with Neutral and Cationic Tantalum Imido Complexes
journal, July 2004

  • Anderson, Laura L.; Arnold, John; Bergman, Robert G.
  • Organic Letters, Vol. 6, Issue 15
  • DOI: 10.1021/ol0492851

Synthesis, Characterization, and Reactions of Isolable (β-Diketiminato)niobium(III) Imido Complexes
journal, November 2010

  • Tomson, Neil C.; Arnold, John; Bergman, Robert G.
  • Organometallics, Vol. 29, Issue 21
  • DOI: 10.1021/om1002528

Structure and Reactivity of Chelating Imido−Amido Complexes of Tantalum. Mechanistic Studies on the Addition of Silanes to Ta−N Multiple Bonds
journal, December 1997

  • Gountchev, Tomislav I.; Tilley, T. Don
  • Journal of the American Chemical Society, Vol. 119, Issue 52
  • DOI: 10.1021/ja9721982

Reactivity of a low-valent chromium dinitrogen complex
journal, April 2011

  • Monillas, Wesley H.; Yap, Glenn P. A.; Theopold, Klaus H.
  • Inorganica Chimica Acta, Vol. 369, Issue 1
  • DOI: 10.1016/j.ica.2010.11.024

An Unusally Diverse Array of Products Formed upon Carbonylation of a Dialkylniobium Complex
journal, August 2008

  • Tomson, Neil C.; Yan, Andrew; Arnold, John
  • Journal of the American Chemical Society, Vol. 130, Issue 34
  • DOI: 10.1021/ja803729k

Kinetics and mechanism of the insertion of olefins into niobium- and tantalum-hydride bonds: a study of the competition between steric and electronic effects
journal, May 1988

  • Burger, Barbara J.; Santarsiero, Bernard D.; Trimmer, Mark S.
  • Journal of the American Chemical Society, Vol. 110, Issue 10
  • DOI: 10.1021/ja00218a023

Unusual κ1 coordination of a β-diketiminate ligand in niobium complexes
journal, January 2016

  • Ziegler, Jessica A.; Bergman, Robert G.; Arnold, John
  • Dalton Transactions, Vol. 45, Issue 32
  • DOI: 10.1039/C6DT02373H

Pendant Arm Functionalized Benzamidinate Titanium Imido Compounds:  Experimental and Computational Studies of Their Reactions with CO 2
journal, May 2005

  • Boyd, Catherine L.; Clot, Eric; Guiducci, Aldo E.
  • Organometallics, Vol. 24, Issue 10
  • DOI: 10.1021/om049026f

Imido-osmium( viii ) compounds in organic synthesis: aminohydroxylation and diamination reactions
journal, January 2004


A reactive organometallic oxo intermediate, Cp*2Zr:O: generation and subsequent trapping reactions forming alkyne and nitrile addition products
journal, November 1989

  • Carney, Michael J.; Walsh, Patrick J.; Hollander, Frederick J.
  • Journal of the American Chemical Society, Vol. 111, Issue 23
  • DOI: 10.1021/ja00205a045

Observation of Inductive Effects That Cause a Change in the Rate-Determining Step for the Conversion of Rhenium Azides to Imido Complexes
journal, October 2011

  • Travia, Nicholas E.; Xu, Zhenggang; Keith, Jason M.
  • Inorganic Chemistry, Vol. 50, Issue 20
  • DOI: 10.1021/ic2017853

Bis(imido)vanadium(V)-Catalyzed [2+2+1] Coupling of Alkynes and Azobenzenes Giving Multisubstituted Pyrroles
journal, February 2019

  • Kawakita, Kento; Beaumier, Evan P.; Kakiuchi, Yuya
  • Journal of the American Chemical Society, Vol. 141, Issue 10
  • DOI: 10.1021/jacs.8b13390

Dihydrogen Activation by Titanium Sulfide Complexes
journal, December 1999

  • Sweeney, Zachary K.; Polse, Jennifer L.; Bergman, Robert G.
  • Organometallics, Vol. 18, Issue 26
  • DOI: 10.1021/om9907876

Halo, Alkyl, Aryl, and Bis(imido) Complexes of Niobium Supported by the β-Diketiminato Ligand
journal, July 2010

  • Tomson, Neil C.; Arnold, John; Bergman, Robert G.
  • Organometallics, Vol. 29, Issue 13
  • DOI: 10.1021/om1001827

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

  • Walsh, Patrick J.; Hollander, Frederick J.; Bergman, Robert G.
  • Journal of the American Chemical Society, Vol. 110, Issue 26
  • DOI: 10.1021/ja00234a043

Methane and benzene activation via transient (tert-Bu3SiNH)2Zr:NSi-tert-Bu3
journal, December 1988

  • Cummins, Christopher C.; Baxter, Steven M.; Wolczanski, Peter T.
  • Journal of the American Chemical Society, Vol. 110, Issue 26
  • DOI: 10.1021/ja00234a044

Carbon–Hydrogen Bond Activation, C–N Bond Coupling, and Cycloaddition Reactivity of a Three-Coordinate Nickel Complex Featuring a Terminal Imido Ligand
journal, November 2014

  • Mindiola, Daniel J.; Waterman, Rory; Iluc, Vlad M.
  • Inorganic Chemistry, Vol. 53, Issue 24
  • DOI: 10.1021/ic5026153

Uranium−Nitrogen Multiple Bonding: The Case of a Four-Coordinate Uranium(VI) Nitridoborate Complex
journal, April 2009

  • Fox, Alexander R.; Cummins, Christopher C.
  • Journal of the American Chemical Society, Vol. 131, Issue 16
  • DOI: 10.1021/ja8095812

The Niobaziridine−Hydride Functional Group:  Synthesis and Divergent Reactivity
journal, April 2003

  • Figueroa, Joshua S.; Cummins, Christopher C.
  • Journal of the American Chemical Society, Vol. 125, Issue 14
  • DOI: 10.1021/ja028446y

Carbodiimide Synthesis via Ti-Catalyzed Nitrene Transfer from Diazenes to Isocyanides
journal, October 2019

  • Beaumier, Evan P.; McGreal, Meghan E.; Pancoast, Adam R.
  • ACS Catalysis, Vol. 9, Issue 12
  • DOI: 10.1021/acscatal.9b04107

Methane Activation by Group VB Bis(imido) Complexes
journal, August 1994


Oxo and Imido Complexes of Rhenium and Molybdenum in Catalytic Reductions
journal, September 2008


Synthesis of a tris(pyrazolyl) borate-stabilized molybdenum alkylidene and its hydrolysis products. Crystal structures of TpMo(CH2C(Me)2Ph) (NAr)(O) and [TpMo(NAr)(O)]2O
journal, January 1995

  • Vaughan, William M.; Abboud, Khalil A.; Boncella, James M.
  • Journal of Organometallic Chemistry, Vol. 485, Issue 1-2
  • DOI: 10.1016/0022-328X(94)24766-C

Ti-Catalyzed Multicomponent Oxidative Carboamination of Alkynes with Alkenes and Diazenes
journal, October 2016

  • Davis-Gilbert, Zachary W.; Yao, Letitia J.; Tonks, Ian A.
  • Journal of the American Chemical Society, Vol. 138, Issue 44
  • DOI: 10.1021/jacs.6b09939

Electron localization in a mixed-valence diniobium benzene complex
journal, January 2015

  • Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.
  • Chemical Science, Vol. 6, Issue 2
  • DOI: 10.1039/C4SC02705A

Synthesis and Reactivity of Dioxazirconacyclohexenes: Development of a Zirconium–Oxo-Mediated Alkyne–Aldehyde Coupling Reaction
journal, March 2015

  • Kortman, Gregory D.; Orr, Meghan J.; Hull, Kami L.
  • Organometallics, Vol. 34, Issue 6
  • DOI: 10.1021/om5008727

Catalytic formal [2+2+1] synthesis of pyrroles from alkynes and diazenes via TiII/TiIV redox catalysis
journal, November 2015

  • Gilbert, Zachary W.; Hue, Ryan J.; Tonks, Ian A.
  • Nature Chemistry, Vol. 8, Issue 1
  • DOI: 10.1038/nchem.2386

Synthesis, Cycloaddition, and Cycloreversion Reactions of Mononuclear Titanocene–oxo Complexes
journal, May 2016


Reactivity of a Terminal Ti(IV) Imido Complex toward Alkenes and Alkynes:  Cycloaddition vs C−H Activation
journal, December 1998

  • Polse, Jennifer L.; Andersen, Richard A.; Bergman, Robert G.
  • Journal of the American Chemical Society, Vol. 120, Issue 51
  • DOI: 10.1021/ja981489n

Reactions of Cyclopentadienyl-Amidinate Titanium Imido Compounds with CS 2 , COS, Isocyanates, and Other Unsaturated Organic Compounds
journal, February 2006

  • Guiducci, Aldo E.; Boyd, Catherine L.; Mountford, Philip
  • Organometallics, Vol. 25, Issue 5
  • DOI: 10.1021/om050784v

Stoichiometric and catalytic hydroamination of alkynes and allene by zirconium bisamides Cp2Zr(NHR)2
journal, February 1992

  • Walsh, Patrick J.; Baranger, Anne M.; Bergman, Robert G.
  • Journal of the American Chemical Society, Vol. 114, Issue 5
  • DOI: 10.1021/ja00031a026

Group 5 Imides and Bis(imide)s as Selective Hydrogenation Catalysts
journal, April 2013

  • Gianetti, Thomas L.; La Pierre, Henry S.; Arnold, John
  • European Journal of Inorganic Chemistry, Vol. 2013, Issue 22-23
  • DOI: 10.1002/ejic.201300202

Reaction of (Bisimido)niobium(V) Complexes with Organic Azides: [3 + 2] Cycloaddition and Reversible Cleavage of β-Diketiminato Ligands Involving Nitrene Transfer
journal, February 2014

  • Obenhuber, Andreas H.; Gianetti, Thomas L.; Berrebi, Xavier
  • Journal of the American Chemical Society, Vol. 136, Issue 8
  • DOI: 10.1021/ja413194z

Phosphaazaallene and phosphinylimide complexes stemming from a terminal and four-coordinate titanium phosphinidene
journal, January 2003

  • Basuli, Falguni; Watson, Lori A.; Huffman, John C.
  • Dalton Trans., Issue 22
  • DOI: 10.1039/B311748K

Transition metal complexes containing organoimido (nr) and related ligands
journal, February 1980


A Mechanistic Study of the Cycloaddition-Cycloreversion Reactions of Zirconium-Imido Complex Cp2Zr(N-t-Bu)(THF) with Organic Imines and Organic Azides
journal, January 1995

  • Meyer, Karen E.; Walsh, Patrick J.; Bergman, Robert G.
  • Journal of the American Chemical Society, Vol. 117, Issue 3
  • DOI: 10.1021/ja00108a014

A Fluorobenzene Adduct of Ti(IV), and Catalytic Carboamination to Prepare α,β-Unsaturated Imines and Triaryl-Substituted Quinolines
journal, December 2005

  • Basuli, Falguni; Aneetha, Halikhedkar; Huffman, John C.
  • Journal of the American Chemical Society, Vol. 127, Issue 51
  • DOI: 10.1021/ja0566026

Room temperature generation of reactive intermediates Cp*Zr:O and Cp*2Zr:S: trapping reactions with unsaturated organic molecules and dative ligands
journal, August 1990

  • Carney, Michael J.; Walsh, Patrick J.; Bergman, Robert G.
  • Journal of the American Chemical Society, Vol. 112, Issue 17
  • DOI: 10.1021/ja00173a057

Multicomponent Pyrazole Synthesis from Alkynes, Nitriles, and Titanium Imido Complexes via Oxidatively Induced N–N Bond Coupling
journal, February 2020

  • Pearce, Adam J.; Harkins, Robin P.; Reiner, Benjamin R.
  • Journal of the American Chemical Society, Vol. 142, Issue 9
  • DOI: 10.1021/jacs.9b13173

Zirconium-Mediated Metathesis of Imines:  A Study of the Scope, Longevity, and Mechanism of a Complicated Catalytic System
journal, February 2000

  • Zuckerman, Rebecca L.; Krska, Shane W.; Bergman, Robert G.
  • Journal of the American Chemical Society, Vol. 122, Issue 5
  • DOI: 10.1021/ja992869r

Z-Selective, Catalytic Internal Alkyne Semihydrogenation under H 2 /CO Mixtures by a Niobium(III) Imido Complex
journal, September 2011

  • Gianetti, Thomas L.; Tomson, Neil C.; Arnold, John
  • Journal of the American Chemical Society, Vol. 133, Issue 38
  • DOI: 10.1021/ja206016s

Olefin metathesis
journal, August 2004


Facile Activation of Triarylboranes by Rhenium(V) Oxo Imido Complexes
journal, April 2020


Titanium Hydrazido and Imido Complexes:  Synthesis, Structure, Reactivity, and Relevance to Alkyne Hydroamination
journal, February 2004

  • Li, Yahong; Shi, Yanhui; Odom, Aaron L.
  • Journal of the American Chemical Society, Vol. 126, Issue 6
  • DOI: 10.1021/ja038320g

Diniobium Inverted Sandwich Complexes with μ-η 66 -Arene Ligands: Synthesis, Kinetics of Formation, and Electronic Structure
journal, February 2013

  • Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.
  • Journal of the American Chemical Society, Vol. 135, Issue 8
  • DOI: 10.1021/ja311966h

Reactivity of a Scandium Terminal Imido Complex Towards Unsaturated Substrates
journal, June 2011

  • Chu, Jiaxiang; Lu, Erli; Liu, Zhixiao
  • Angewandte Chemie International Edition, Vol. 50, Issue 33
  • DOI: 10.1002/anie.201102267

Syntheses and structures of thermally stable diketiminato complexes of gold and copper
journal, January 2011

  • Carrera, Nora; Savjani, Nicky; Simpson, Jason
  • Dalton Trans., Vol. 40, Issue 5
  • DOI: 10.1039/C0DT01422B

Lewis Acid Triggered Reactivity of a Lewis Base Stabilized Scandium-Terminal Imido Complex: C–H Bond Activation, Cycloaddition, and Dehydrofluorination
journal, July 2014

  • Chu, Jiaxiang; Han, Xianghao; Kefalidis, Christos E.
  • Journal of the American Chemical Society, Vol. 136, Issue 31
  • DOI: 10.1021/ja5061559

The catalytic hydroamination of alkynes
journal, January 2003

  • Pohlki, Frauke; Doye, Sven
  • Chemical Society Reviews, Vol. 32, Issue 2
  • DOI: 10.1039/b200386b

Use of Steric Hindrance and a Metallacyclobutene Resting State to Develop Robust and Kinetically Characterizable Zirconium-Based Imine Metathesis Catalysts
journal, November 1998

  • Krska, Shane W.; Zuckerman, Rebecca L.; Bergman, Robert G.
  • Journal of the American Chemical Society, Vol. 120, Issue 45
  • DOI: 10.1021/ja982569u

Aryl Isocyanate, Carbodiimide, and Isocyanide Prepared from Carbon Dioxide. A Metathetical Group-Transfer Tale Involving a Titanium−Imide Zwitterion
journal, January 2006

  • Kilgore, Uriah J.; Basuli, Falguni; Huffman, John C.
  • Inorganic Chemistry, Vol. 45, Issue 2
  • DOI: 10.1021/ic052065e

Selective transformations of organic compounds by imidozirconocene complexes
journal, November 2002

  • Duncan, Andrew P.; Bergman, Robert G.
  • The Chemical Record, Vol. 2, Issue 6
  • DOI: 10.1002/tcr.10039

Synthesis and reactivity of cationic niobium and tantalum methyl complexes supported by imido and β-diketiminato ligands
journal, January 2011

  • Tomson, Neil C.; Arnold, John; Bergman, Robert G.
  • Dalton Transactions, Vol. 40, Issue 30
  • DOI: 10.1039/c1dt10202h

Generation of the highly reactive intermediates Cp*2Zr:O and Cp*2Zr:S: trapping reactions with alkynes, nitriles, and dative ligands
journal, February 1992

  • Carney, Michael J.; Walsh, Patrick J.; Hollander, Frederick J.
  • Organometallics, Vol. 11, Issue 2
  • DOI: 10.1021/om00038a040

Terminal zirconium oxo complexes: synthesis, structure, and reactivity of (.eta.5-C5Me4R)2Zr(O)(NC5H4R')
journal, June 1993

  • Howard, William A.; Waters, Marcey; Parkin, Gerard
  • Journal of the American Chemical Society, Vol. 115, Issue 11
  • DOI: 10.1021/ja00064a074

Group 5 chemistry supported by β-diketiminate ligands
journal, January 2016

  • Hohloch, Stephan; Kriegel, Benjamin M.; Bergman, Robert G.
  • Dalton Transactions, Vol. 45, Issue 40
  • DOI: 10.1039/C6DT01770C

Photo-activation of d 0 niobium imido azides: en route to nitrido complexes
journal, January 2016

  • Camp, Clément; Grant, Lauren N.; Bergman, Robert G.
  • Chemical Communications, Vol. 52, Issue 32
  • DOI: 10.1039/C6CC02081J

Terminal chalcogenido complexes of zirconium: Syntheses and reactivity of Cp2*Zr(E)(NC5H5) (E = O, S, Se, Te)
journal, February 1997


Catalytic Asymmetric Dihydroxylation
journal, December 1994

  • Kolb, Hartmuth C.; VanNieuwenhze, Michael S.; Sharpless, K. Barry
  • Chemical Reviews, Vol. 94, Issue 8
  • DOI: 10.1021/cr00032a009

ORTEP -3 for Windows - a version of ORTEP -III with a Graphical User Interface (GUI)
journal, October 1997


The structure and chemistry of tris(pentafluorophenyl)borane protected mononuclear nitridotitanium complexes
journal, January 2012

  • Fuller, Anna-Marie; Hughes, David L.; Jones, Garth A.
  • Dalton Transactions, Vol. 41, Issue 18
  • DOI: 10.1039/c2dt00056c

Mercury CSD 2.0 – new features for the visualization and investigation of crystal structures
journal, March 2008

  • Macrae, Clare F.; Bruno, Ian J.; Chisholm, James A.
  • Journal of Applied Crystallography, Vol. 41, Issue 2
  • DOI: 10.1107/S0021889807067908

Geminal coupling constants in methylene groups—III
journal, January 1969


Structure validation in chemical crystallography
journal, January 2009

  • Spek, Anthony L.
  • Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155
  • DOI: 10.1107/S090744490804362X

{2 + 2} Cycloaddition of Alkyne with Titanium−Imido Complex: Theoretical Study of Determining Factor of Reactivity and Regioselectivity
journal, January 2010

  • Ochi, Noriaki; Nakao, Yoshihide; Sato, Hirofumi
  • The Journal of Physical Chemistry A, Vol. 114, Issue 1
  • DOI: 10.1021/jp908465b

Terminal Titanium-Ligand Multiple Bonds. Cleavages of CO and CS Double Bonds with Ti Imido Complexes
journal, October 2004

  • Hsu, Shih-Hsien; Chang, Jr-Chiuan; Lai, Chun-Liang
  • Inorganic Chemistry, Vol. 43, Issue 21
  • DOI: 10.1021/ic049474f

Carbon–fluorine bond cleavage in fluoroarenes via a niobium(iii) imido complex: from stoichiometric to catalytic hydrodefluorination
journal, January 2014

  • Gianetti, Thomas L.; Bergman, Robert G.; Arnold, John
  • Chemical Science, Vol. 5, Issue 6
  • DOI: 10.1039/c4sc00006d

Dioxo-, Oxo-imido-, and Bis-imido-Molybdenum(VI) Complexes with a Bis-phenolate-NHC Ligand
journal, September 2019


A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Nitrene Metathesis and Catalytic Nitrene Transfer Promoted by Niobium Bis(imido) Complexes
journal, December 2015

  • Kriegel, Benjamin M.; Bergman, Robert G.; Arnold, John
  • Journal of the American Chemical Society, Vol. 138, Issue 1
  • DOI: 10.1021/jacs.5b11287

Synthesis and Characterization of Three-Coordinate Ni(III)-Imide Complexes
journal, August 2011

  • Iluc, Vlad M.; Miller, Alexander J. M.; Anderson, John S.
  • Journal of the American Chemical Society, Vol. 133, Issue 33
  • DOI: 10.1021/ja2024993

Synthesis and molecular structure of the niobocene sulphide dimer
journal, June 1984

  • Skripkin, Yu. V.; Eremenko, I. L.; Pasynskii, A. A.
  • Journal of Organometallic Chemistry, Vol. 267, Issue 3
  • DOI: 10.1016/0022-328X(84)80200-4

Cycloaddition and Cycloreversion Reactions of a Monomeric Ti(IV) Oxo Complex with Terminal and Internal Alkynes. A Reversible Oxametallacyclobutene/Hydroxoacetylide Interconversion
journal, May 1995

  • Polse, Jennifer L.; Andersen, Richard A.; Bergman, Robert G.
  • Journal of the American Chemical Society, Vol. 117, Issue 19
  • DOI: 10.1021/ja00124a036

Reversible Addition of the Si–H Bond of Phenylsilane to the Sc═N Bond of a Scandium Terminal Imido Complex
journal, December 2012

  • Chu, Jiaxiang; Lu, Erli; Chen, Yaofeng
  • Organometallics, Vol. 32, Issue 5
  • DOI: 10.1021/om3010349

Reactions and Applications of Titanium Imido Complexes
journal, November 2005

  • Hazari, Nilay; Mountford, Philip
  • Accounts of Chemical Research, Vol. 38, Issue 11
  • DOI: 10.1021/ar030244z

Titanium-Catalyzed Multicomponent Couplings: Efficient One-Pot Syntheses of Nitrogen Heterocycles
journal, August 2015


Cycloaddition reactions of titanium and zirconium imido, oxo and hydrazido complexes supported by tetraaza macrocyclic ligands ‡
journal, January 1999

  • Blake, Alexander J.; McInnes, Jacqueline M.; Mountford, Philip
  • Journal of the Chemical Society, Dalton Transactions, Issue 3
  • DOI: 10.1039/a806827e

Novel double substrate insertion versus isocyanate extrusion in reactions of imidotitanium complexes with CO2: critical dependence on imido N-substituents †
journal, January 2001

  • Guiducci, Aldo E.; Cowley, Andrew R.; Skinner, Michael E. G.
  • Journal of the Chemical Society, Dalton Transactions, Issue 9
  • DOI: 10.1039/b102704m

Regioselective [2+2] and [4+2] cycloaddition reactivity in an asymmetric niobium(bisimido) moiety towards unsaturated organic molecules
journal, January 2015

  • Obenhuber, A. H.; Gianetti, T. L.; Bergman, R. G.
  • Chemical Communications, Vol. 51, Issue 7
  • DOI: 10.1039/C4CC07851A

Small Molecule Activation Mediated by a Thorium Terminal Imido Metallocene
journal, July 2015


Direct Hydride/Silyl Exchange— Synthesis and X-ray Study of the Bis(silyl) Complex [Cp2NbH(SiCl3)2]
journal, February 2004

  • Dorogov, Konstantin Yu.; Churakov, Andrei V.; Kuzmina, Lyudmila G.
  • European Journal of Inorganic Chemistry, Vol. 2004, Issue 4
  • DOI: 10.1002/ejic.200300134

Carboamination: Additions of Imine CN Bonds Across Alkynes Catalyzed by Imidozirconium Complexes
journal, October 2004

  • Ruck, Rebecca T.; Zuckerman, Rebecca L.; Krska, Shane W.
  • Angewandte Chemie International Edition, Vol. 43, Issue 40
  • DOI: 10.1002/anie.200461063

Zirconium-Mediated Imine Metathesis. Synthesis of 2,4-Diaza-1-zirconiacyclobutanes and the Mechanism of Their Reactions with Imines and Alkynes
journal, March 1994

  • Meyer, Karen E.; Walsh, Patrick J.; Bergman, Robert G.
  • Journal of the American Chemical Society, Vol. 116, Issue 6
  • DOI: 10.1021/ja00085a077

Diamination of Olefins: Synthesis, Structures and Reactivity of Osmaimidazolidines
journal, November 2003

  • Muñiz, Kilian; Iesato, Atsushi; Nieger, Martin
  • Chemistry - A European Journal, Vol. 9, Issue 22
  • DOI: 10.1002/chem.200305011

Catalytic nitrene transfer by a zirconium( iv ) redox-active ligand complex
journal, January 2011

  • Nguyen, Andy I.; Zarkesh, Ryan A.; Lacy, David C.
  • Chem. Sci., Vol. 2, Issue 1
  • DOI: 10.1039/C0SC00414F

Variable regiochemistry in the stoichiometric and catalytic hydroamination of alkynes by imidozirconium complexes caused by an unusual dependence of the rate law on alkyne structure and temperature
journal, April 1993

  • Baranger, Anne M.; Walsh, Patrick J.; Bergman, Robert G.
  • Journal of the American Chemical Society, Vol. 115, Issue 7
  • DOI: 10.1021/ja00060a025

1,2-Addition versus σ-Bond Metathesis Reactions in Transient Bis(cyclopentadienyl)zirconium Imides: Evidence for a d 0 Dihydrogen Complex
journal, March 2008

  • Toomey, Hannah E.; Pun, Doris; Veiros, Luis F.
  • Organometallics, Vol. 27, Issue 5
  • DOI: 10.1021/om7010485

Z -Selective Semihydrogenation of Alkynes Catalyzed by a Cationic Vanadium Bisimido Complex
journal, March 2011

  • La Pierre, Henry S.; Arnold, John; Toste, F. Dean
  • Angewandte Chemie International Edition, Vol. 50, Issue 17
  • DOI: 10.1002/anie.201007876