Carbon–Hydrogen Bond Activation, C–N Bond Coupling, and Cycloaddition Reactivity of a Three-Coordinate Nickel Complex Featuring a Terminal Imido Ligand
Abstract
Here, the three-coordinate imidos (dtbpe)Ni=NR (dtbpe = tBu2PCH2CH2PtBu2, R = 2,6-iPr2C6H3, 2,4,6-Me3C6H2 (Mes), and 1-adamantyl (Ad)), which contain a legitimate Ni–N double bond as well as basic imido nitrogen based on theoretical analysis, readily deprotonate HC≡CPh to form the amide acetylide species (dtbpe)Ni{NH(Ar)}(C≡CPh). In the case of R = 2,6-iPr2C6H3, reductive carbonylation results in formation of the (dtbpe)Ni(CO)2 along with the N–C coupled product keteneimine PhCH=C=N(2,6- iPr2C6H3). Given the ability of the Ni=N bond to have biradical character as suggested by theoretical analysis, H atom abstraction can also occur in (dtbpe)Ni=N{2,6-iPr2C6H3} when this species is treated with HSn(nBu)3. Likewise, the microscopic reverse reaction—conversion of the Ni(I) anilide (dtbpe)Ni{NH(2,6-iPr2C6H3)} to the imido (dtbpe)Ni=N{2,6-iPr2C6H3}—is promoted when using the radical Mes*O• (Mes* = 2,4,6-tBu3C6H2). Reactivity studies involving the imido complexes, in particular (dtbpe)Ni=N{2,6-iPr2C6H3}, are also reported with small, unsaturated molecules such as diphenylketene, benzylisocyanate, benzaldehyde, and carbon dioxide, including the formation of C–N and N–N bonds by coupling reactions. In addition to NMR spectroscopic data and combustion analysis, we also report structural studies for all the cycloaddition reactions involving the imido (dtbpe)Ni=N{2,6-iPr2C6H3}.
- Authors:
-
- Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States
- Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States, Department of Chemistry, Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas, Denton, Texas 76203, United States
- Publication Date:
- Research Org.:
- Univ. of North Texas, Denton, TX (United States); Univ. of Chicago, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1165390
- Alternate Identifier(s):
- OSTI ID: 1345643
- Grant/Contract Number:
- FG02-03ER15387
- Resource Type:
- Published Article
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Name: Inorganic Chemistry Journal Volume: 53 Journal Issue: 24; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Mindiola, Daniel J., Waterman, Rory, Iluc, Vlad M., Cundari, Thomas R., and Hillhouse, Gregory L. Carbon–Hydrogen Bond Activation, C–N Bond Coupling, and Cycloaddition Reactivity of a Three-Coordinate Nickel Complex Featuring a Terminal Imido Ligand. United States: N. p., 2014.
Web. doi:10.1021/ic5026153.
Mindiola, Daniel J., Waterman, Rory, Iluc, Vlad M., Cundari, Thomas R., & Hillhouse, Gregory L. Carbon–Hydrogen Bond Activation, C–N Bond Coupling, and Cycloaddition Reactivity of a Three-Coordinate Nickel Complex Featuring a Terminal Imido Ligand. United States. https://doi.org/10.1021/ic5026153
Mindiola, Daniel J., Waterman, Rory, Iluc, Vlad M., Cundari, Thomas R., and Hillhouse, Gregory L. Mon .
"Carbon–Hydrogen Bond Activation, C–N Bond Coupling, and Cycloaddition Reactivity of a Three-Coordinate Nickel Complex Featuring a Terminal Imido Ligand". United States. https://doi.org/10.1021/ic5026153.
@article{osti_1165390,
title = {Carbon–Hydrogen Bond Activation, C–N Bond Coupling, and Cycloaddition Reactivity of a Three-Coordinate Nickel Complex Featuring a Terminal Imido Ligand},
author = {Mindiola, Daniel J. and Waterman, Rory and Iluc, Vlad M. and Cundari, Thomas R. and Hillhouse, Gregory L.},
abstractNote = {Here, the three-coordinate imidos (dtbpe)Ni=NR (dtbpe = tBu2PCH2CH2PtBu2, R = 2,6-iPr2C6H3, 2,4,6-Me3C6H2 (Mes), and 1-adamantyl (Ad)), which contain a legitimate Ni–N double bond as well as basic imido nitrogen based on theoretical analysis, readily deprotonate HC≡CPh to form the amide acetylide species (dtbpe)Ni{NH(Ar)}(C≡CPh). In the case of R = 2,6-iPr2C6H3, reductive carbonylation results in formation of the (dtbpe)Ni(CO)2 along with the N–C coupled product keteneimine PhCH=C=N(2,6- iPr2C6H3). Given the ability of the Ni=N bond to have biradical character as suggested by theoretical analysis, H atom abstraction can also occur in (dtbpe)Ni=N{2,6-iPr2C6H3} when this species is treated with HSn(nBu)3. Likewise, the microscopic reverse reaction—conversion of the Ni(I) anilide (dtbpe)Ni{NH(2,6-iPr2C6H3)} to the imido (dtbpe)Ni=N{2,6-iPr2C6H3}—is promoted when using the radical Mes*O• (Mes* = 2,4,6-tBu3C6H2). Reactivity studies involving the imido complexes, in particular (dtbpe)Ni=N{2,6-iPr2C6H3}, are also reported with small, unsaturated molecules such as diphenylketene, benzylisocyanate, benzaldehyde, and carbon dioxide, including the formation of C–N and N–N bonds by coupling reactions. In addition to NMR spectroscopic data and combustion analysis, we also report structural studies for all the cycloaddition reactions involving the imido (dtbpe)Ni=N{2,6-iPr2C6H3}.},
doi = {10.1021/ic5026153},
journal = {Inorganic Chemistry},
number = 24,
volume = 53,
place = {United States},
year = {Mon Dec 01 00:00:00 EST 2014},
month = {Mon Dec 01 00:00:00 EST 2014}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/ic5026153
https://doi.org/10.1021/ic5026153
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 47 works
Citation information provided by
Web of Science
Web of Science
Figures / Tables:
Scheme 1: Terminal Coordinated Ni$=$N-type Complexes of Nickel
All figures and tables
(14 total)
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Oxidative Group Transfer to Co(I) Affords a Terminal Co(III) Imido Complex
journal, September 2002
- Jenkins, David M.; Betley, Theodore A.; Peters, Jonas C.
- Journal of the American Chemical Society, Vol. 124, Issue 38
C–H Functionalization Reactivity of a Nickel–Imide
journal, June 2012
- Wiese, Stefan; McAfee, Jason L.; Pahls, Dale R.
- Journal of the American Chemical Society, Vol. 134, Issue 24
UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
journal, December 1992
- Rappe, A. K.; Casewit, C. J.; Colwell, K. S.
- Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035
Hindered Brønsted bases as Lewis base catalysts
journal, January 2009
- Tabassum, Sobia; Sereda, Oksana; Reddy, Peddiahgari Vasu Govardhana
- Organic & Biomolecular Chemistry, Vol. 7, Issue 19
Snapshots of Complete Nitrogen Atom Transfer from an Iron(IV) Nitrido Complex
journal, June 2011
- Scepaniak, Jeremiah J.; Bontchev, Ranko P.; Johnson, Dennis L.
- Angewandte Chemie International Edition, Vol. 50, Issue 29
Late Transition Metal .mu.-Oxo and .mu.-Imido Complexes. 15. Oxidative Coupling of Rhodium Phenyl Imido/Amido Complexes
journal, September 1994
- Ge, Yuan-Wen; Ye, Yao; Sharp, Paul R.
- Journal of the American Chemical Society, Vol. 116, Issue 18
Synthesis, Structure, and Reactions of a Three-Coordinate Nickel-Carbene Complex, {1,2-Bis(di- tert -butylphosphino)ethane}NiCPh 2
journal, August 2002
- Mindiola, Daniel J.; Hillhouse, Gregory L.
- Journal of the American Chemical Society, Vol. 124, Issue 34
Application of the E-C Approach to Understanding the Bond Energies Thermodynamics of Late-Metal Amido, Aryloxo and Alkoxo Complexes: An Alternative to pπ/dπ Repulsion
journal, April 1999
- Holland, Patrick L.; Andersen, Richard A.; Bergman, Robert G.
- Comments on Inorganic Chemistry, Vol. 21, Issue 1-3
Late Transition Metal Oxo and Imido Chemistry
journal, April 1999
- Sharp, Paul R.
- Comments on Inorganic Chemistry, Vol. 21, Issue 1-3
A new ONIOM implementation in Gaussian98. Part I. The calculation of energies, gradients, vibrational frequencies and electric field derivatives
journal, April 1999
- Dapprich, Stefan; Komáromi, István; Byun, K. Suzie
- Journal of Molecular Structure: THEOCHEM, Vol. 461-462
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980
- Krishnan, R.; Binkley, J. S.; Seeger, R.
- The Journal of Chemical Physics, Vol. 72, Issue 1
Equilibrium acidities of carbon acids. VI. Establishment of an absolute scale of acidities in dimethyl sulfoxide solution
journal, November 1975
- Matthews, Walter S.; Bares, Joseph E.; Bartmess, John E.
- Journal of the American Chemical Society, Vol. 97, Issue 24
Carbon−Heteroatom Bond-Forming Reductive Eliminations of Amines, Ethers, and Sulfides
journal, December 1998
- Hartwig, John F.
- Accounts of Chemical Research, Vol. 31, Issue 12
Reductive Deprotonation and Dehydrogenation of Phenylhydrazine at a Nickel Center To Give a Nickel Diazenido Complex
journal, September 2012
- Köthe, Claudia; Metzinger, Ramona; Herwig, Christian
- Inorganic Chemistry, Vol. 51, Issue 18
Reduction of Organic Compounds by Lithium Aluminum Hydride. III. Halides, Quinones, Miscellaneous Nitrogen Compounds 1
journal, November 1948
- Nystrom, Robert F.; Brown, Weldon G.
- Journal of the American Chemical Society, Vol. 70, Issue 11
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007
- Zhao, Yan; Truhlar, Donald G.
- Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
400. The determination of the paramagnetic susceptibility of substances in solution by nuclear magnetic resonance
journal, January 1959
- Evans, D. F.
- Journal of the Chemical Society (Resumed)
Structural Characterization and Intramolecular Aliphatic C−H Oxidation Ability of MIII(μ-O)2MIII Complexes of Ni and Co with the Hydrotris(3,5-dialkyl-4-X-pyrazolyl)borate Ligands TpMe2,X (X=Me, H, Br) and TpiPr2
journal, December 2001
- Hikichi, Shiro; Yoshizawa, Michito; Sasakura, Yasuyuki
- Chemistry - A European Journal, Vol. 7, Issue 23
Rational Development of Practical Catalysts for Aromatic Carbon−Nitrogen Bond Formation
journal, December 1998
- Wolfe, John P.; Wagaw, Seble; Marcoux, Jean-François
- Accounts of Chemical Research, Vol. 31, Issue 12
A Terminal Ni(III)−Imide with Diverse Reactivity Pathways
journal, August 2005
- Kogut, Elzbieta; Wiencko, Heather L.; Zhang, Libei
- Journal of the American Chemical Society, Vol. 127, Issue 32
Mechanism of Catalytic Nitrene Transfer Using Iron(I)–Isocyanide Complexes
journal, September 2013
- Cowley, Ryan E.; Golder, Matthew R.; Eckert, Nathan A.
- Organometallics, Vol. 32, Issue 19
The Construction and Interpretation of Mcscf Wavefunctions
journal, October 1998
- Schmidt, Michael W.; Gordon, Mark S.
- Annual Review of Physical Chemistry, Vol. 49, Issue 1
Bis(di-tert-butylphosphino)ethan-nickel(0)-Komplexe / Bis(di-tert-butylphosphino)ethane-nickel(0) Complexes
journal, May 1993
- Pörschke, Klaus-Richard; Pluta, Christian; Proft, Bernd
- Zeitschrift für Naturforschung B, Vol. 48, Issue 5
Group-Transfer Reactions of Nickel−Carbene and −Nitrene Complexes with Organoazides and Nitrous Oxide that Form New C═N, C═O, and N═N Bonds
journal, September 2009
- Harrold, Nicole D.; Waterman, Rory; Hillhouse, Gregory L.
- Journal of the American Chemical Society, Vol. 131, Issue 36
Interactions of Aziridines with Nickel Complexes: Oxidative-Addition and Reductive-Elimination Reactions that Break and Make C−N Bonds
journal, March 2002
- Lin, Beatrice L.; Clough, Christopher R.; Hillhouse, Gregory L.
- Journal of the American Chemical Society, Vol. 124, Issue 12
Group Transfer from Nickel Imido, Phosphinidene, and Carbene Complexes to Ethylene with Formation of Aziridine, Phosphirane, and Cyclopropane Products
journal, November 2003
- Waterman, Rory; Hillhouse, Gregory L.
- Journal of the American Chemical Society, Vol. 125, Issue 44
Arrested 1,2-Hydrogen Migration from Silicon to Nickel upon Oxidation of a Three-Coordinate Ni(I) Silyl Complex
journal, September 2010
- Iluc, Vlad M.; Hillhouse, Gregory L.
- Journal of the American Chemical Society, Vol. 132, Issue 34
Oxygen-Induced Ligand Dehydrogenation of a Planar Bis-μ-Chloronickel(I) Dimer Featuring an NHC Ligand
journal, May 2005
- Dible, Benjamin R.; Sigman, Matthew S.; Arif, Atta M.
- Inorganic Chemistry, Vol. 44, Issue 11
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
Catalytic nitrene transfer from an imidoiron(iii) complex to form carbodiimides and isocyanates
journal, January 2009
- Cowley, Ryan E.; Eckert, Nathan A.; Elhaïk, Jérôme
- Chemical Communications, Issue 13
η 2 -Organoazide Complexes of Nickel and Their Conversion to Terminal Imido Complexes via Dinitrogen Extrusion
journal, September 2008
- Waterman, Rory; Hillhouse, Gregory L.
- Journal of the American Chemical Society, Vol. 130, Issue 38
General atomic and molecular electronic structure system
journal, November 1993
- Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
- Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
Hydrogen-Atom Abstraction from Ni(I) Phosphido and Amido Complexes Gives Phosphinidene and Imide Ligands
journal, November 2010
- Iluc, Vlad M.; Hillhouse, Gregory L.
- Journal of the American Chemical Society, Vol. 132, Issue 43
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
Synthesis of 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) complexes of nickel: radical coupling and reduction reactions promoted by the nickel(I) dimer [(dtbpe)NiCl]2
journal, March 2003
- Mindiola, Daniel J.; Waterman, Rory; Jenkins, David M.
- Inorganica Chimica Acta, Vol. 345
Safe and Convenient Procedure for Solvent Purification
journal, January 1996
- Pangborn, Amy B.; Giardello, Michael A.; Grubbs, Robert H.
- Organometallics, Vol. 15, Issue 5, p. 1518-1520
.eta.2-(C,O) Ketene coordination at nickel(O). Synthesis, bonding, and molecular structure of (dtbpm)Ni[.eta.2-(C,O)-Ph2C2O] [dtbpm = bis(di-tert-butylphosphino)methane]
journal, March 1992
- Hofmann, Peter; Perez-Moya, Luis A.; Steigelmann, Oliver
- Organometallics, Vol. 11, Issue 3
Reactions and Applications of Titanium Imido Complexes
journal, November 2005
- Hazari, Nilay; Mountford, Philip
- Accounts of Chemical Research, Vol. 38, Issue 11
Terminal Amido and Imido Complexes of Three-Coordinate Nickel
journal, May 2001
- Mindiola, Daniel J.; Hillhouse, Gregory L.
- Journal of the American Chemical Society, Vol. 123, Issue 19
Formation of Phosphirenes by Phosphinidene Group-Transfer Reactions from (dtbpe)NiP(dmp) to Alkynes
journal, December 2003
- Waterman, Rory; Hillhouse, Gregory L.
- Organometallics, Vol. 22, Issue 25
Flash Photolytic Generation of Primary, Secondary, and Tertiary Ynamines in Aqueous Solution and Study of Their Carbon-Protonation Reactions in That Medium
journal, January 1996
- Chiang, Y.; Grant, A. S.; Kresge, A. J.
- Journal of the American Chemical Society, Vol. 118, Issue 18
Strongly bent nickel imides supported by a chelating bis(N-heterocyclic carbene) ligand
journal, January 2013
- Harrold, Nicole D.; Hillhouse, Gregory L.
- Chemical Science, Vol. 4, Issue 10
β-Diketiminato Nickel Imides in Catalytic Nitrene Transfer to Isocyanides
journal, April 2013
- Wiese, Stefan; Aguila, Mae Joanne B.; Kogut, Elzbieta
- Organometallics, Vol. 32, Issue 8
Metallaoxetanes as possible intermediates in metal-promoted deoxygenation of epoxides and epoxidation of olefins
journal, January 1992
- Baeckvall, Jan E.; Boekman, Fredrik; Blomberg, Margareta R. A.
- Journal of the American Chemical Society, Vol. 114, Issue 2
A “Side-on” Superoxonickel Complex [LNi(O 2 )] with a Square-Planar Tetracoordinate Nickel(II) Center and Its Conversion into [LNi(μ-OH) 2 NiL]
journal, September 2008
- Yao, Shenglai; Bill, Eckhard; Milsmann, Carsten
- Angewandte Chemie International Edition, Vol. 47, Issue 37
Isocyanate and carbodiimide synthesis by nitrene-group-transfer from a nickel(ii) imido complexElectronic supplementary information (ESI) available: complete experimental, spectroscopic, analytical, and crystallographic details. See http://www.rsc.org/suppdata/cc/b2/b204846a/
journal, July 2002
- Mindiola, Daniel J.; Hillhouse, Gregory L.
- Chemical Communications, Issue 17
Fluoroalkylimido-complexes of group VIII metals
journal, January 1970
- McGlinchey, M. J.; Stone, F. G. A.
- Journal of the Chemical Society D: Chemical Communications, Issue 19
Reactivity of Tris(trimethylsilyl)silane toward Diarylaminyl Radicals
journal, August 2001
- Varlamov, Vladimir T.; Denisov, Evguenii T.; Chatgilialoglu, Chryssostomos
- The Journal of Organic Chemistry, Vol. 66, Issue 19
Formation of a Cobalt(III) Imido from a Cobalt(II) Amido Complex. Evidence for Proton-Coupled Electron Transfer
journal, March 2007
- Cowley, Ryan E.; Bontchev, Ranko P.; Sorrell, John
- Journal of the American Chemical Society, Vol. 129, Issue 9
Sequential Reaction Intermediates in Aliphatic C−H Bond Functionalization Initiated by a Bis(μ-oxo)dinickel(III) Complex
journal, April 2006
- Cho, Jaeheung; Furutachi, Hideki; Fujinami, Shuhei
- Inorganic Chemistry, Vol. 45, Issue 7
Formation of CC and CN Bonds in NiII Ketimide Complexes via Transient NiIII Aryl Imides
journal, March 2007
- Bai, Guangcai; Stephan, Douglas W.
- Angewandte Chemie International Edition, Vol. 46, Issue 11
Catalytic C−H Bond Amination from High-Spin Iron Imido Complexes
journal, April 2011
- King, Evan R.; Hennessy, Elisabeth T.; Betley, Theodore A.
- Journal of the American Chemical Society, Vol. 133, Issue 13
Synthesis, Structures, and Properties of Bis( μ -oxo)nickel(III) and Bis( μ -superoxo)nickel(II) Complexes: An Unusual Conversion of a Ni III 2 ( μ -O) 2 Core into a Ni II 2 ( μ -OO) 2 Core by H 2 O 2 and Oxygenation of Ligand
journal, January 2000
- Shiren, Kazushi; Ogo, Seiji; Fujinami, Shuhei
- Journal of the American Chemical Society, Vol. 122, Issue 2
Group-Transfer Reactions of Ni(II)−Ni(II) Bridging Imido Complexes. Catalytic Formation of Carbodiimides and Isocyanates via Nitrene Transfer from Organoazides
journal, October 2009
- Laskowski, Carl A.; Hillhouse, Gregory L.
- Organometallics, Vol. 28, Issue 20
Catalytic Tuning of a Phosphinoethane Ligand for Enhanced C−H Activation
journal, September 2008
- Cundari, Thomas R.; Jimenez-Halla, J. Oscar C.; Morello, Glenn R.
- Journal of the American Chemical Society, Vol. 130, Issue 39
A Two-Coordinate Nickel Imido Complex That Effects C−H Amination
journal, February 2011
- Laskowski, Carl A.; Miller, Alexander J. M.; Hillhouse, Gregory L.
- Journal of the American Chemical Society, Vol. 133, Issue 4
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.