Photolysis of Tp'Rh(CNneopentyl)(PhNCNneopentyl) in the presence of ketones and esters: kinetic and thermodynamic selectivity for activation of different aliphatic C–H bonds
Abstract
The competitive fragment [Tp'Rh(CNneopentyl)], generated from the precursor Tp'Rh(CNneopentyl)(PhNCNneopentyl), underwent oxidative addition of substituted ketones and esters resulting in Tp'Rh(CNneopentyl)(R)(H) complexes (Tp' = tris-(3,5-dimethylpyrazolyl)borate). These C–H activated complexes underwent reductive elimination at varying temperatures (24–70 °C) in C6D6 or C6D12. Using previously established kinetic techniques, the relative Rh–C bond strengths were calculated. Analysis of the relative Rh–C bond strengths vs. C–H bond strengths demonstrates a linear correlation with slope RM–C/C–H = 1.22 (12). In general, α-substituents increase the relative Rh–C bond strengths compared to the C–H bond that is broken.
- Publication Date:
- Research Org.:
- Univ. of Rochester, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1617200
- Alternate Identifier(s):
- OSTI ID: 1525503
- Grant/Contract Number:
- FG02-86ER13569; DGE-1419118
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 48; Journal Issue: 29; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; rhodium; C-H activation; selectivity; ketone; ester
Citation Formats
Parsons, Astrid M., and Jones, William D. Photolysis of Tp'Rh(CNneopentyl)(PhNCNneopentyl) in the presence of ketones and esters: kinetic and thermodynamic selectivity for activation of different aliphatic C–H bonds. United States: N. p., 2019.
Web. doi:10.1039/C9DT01802F.
Parsons, Astrid M., & Jones, William D. Photolysis of Tp'Rh(CNneopentyl)(PhNCNneopentyl) in the presence of ketones and esters: kinetic and thermodynamic selectivity for activation of different aliphatic C–H bonds. United States. https://doi.org/10.1039/C9DT01802F
Parsons, Astrid M., and Jones, William D. Mon .
"Photolysis of Tp'Rh(CNneopentyl)(PhNCNneopentyl) in the presence of ketones and esters: kinetic and thermodynamic selectivity for activation of different aliphatic C–H bonds". United States. https://doi.org/10.1039/C9DT01802F. https://www.osti.gov/servlets/purl/1617200.
@article{osti_1617200,
title = {Photolysis of Tp'Rh(CNneopentyl)(PhNCNneopentyl) in the presence of ketones and esters: kinetic and thermodynamic selectivity for activation of different aliphatic C–H bonds},
author = {Parsons, Astrid M. and Jones, William D.},
abstractNote = {The competitive fragment [Tp'Rh(CNneopentyl)], generated from the precursor Tp'Rh(CNneopentyl)(PhNCNneopentyl), underwent oxidative addition of substituted ketones and esters resulting in Tp'Rh(CNneopentyl)(R)(H) complexes (Tp' = tris-(3,5-dimethylpyrazolyl)borate). These C–H activated complexes underwent reductive elimination at varying temperatures (24–70 °C) in C6D6 or C6D12. Using previously established kinetic techniques, the relative Rh–C bond strengths were calculated. Analysis of the relative Rh–C bond strengths vs. C–H bond strengths demonstrates a linear correlation with slope RM–C/C–H = 1.22 (12). In general, α-substituents increase the relative Rh–C bond strengths compared to the C–H bond that is broken.},
doi = {10.1039/C9DT01802F},
journal = {Dalton Transactions},
number = 29,
volume = 48,
place = {United States},
year = {Mon May 27 00:00:00 EDT 2019},
month = {Mon May 27 00:00:00 EDT 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 2 works
Citation information provided by
Web of Science
Web of Science
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:
C–H bond activation enables the rapid construction and late-stage diversification of functional molecules
journal, April 2013
- Wencel-Delord, Joanna; Glorius, Frank
- Nature Chemistry, Vol. 5, Issue 5
Recent applications of C–H functionalization in complex natural product synthesis
journal, January 2018
- Abrams, Dylan J.; Provencher, Philip A.; Sorensen, Erik J.
- Chemical Society Reviews, Vol. 47, Issue 23
Activation of carbon-hydrogen bonds in saturated hydrocarbons on photolysis of (.eta.5-C5Me5)(PMe3)IrH2. Relative rates of reaction of the intermediate with different types of carbon-hydrogen bonds and functionalization of the metal-bound alkyl groups
journal, June 1983
- Janowicz, Andrew H.; Bergman, Robert G.
- Journal of the American Chemical Society, Vol. 105, Issue 12
A structural, kinetic and thermodynamic study of the reversible thermal carbon-hydrogen bond activation/reductive elimination of alkanes at iridium
journal, April 1986
- Buchanan, J. Michael.; Stryker, Jeffrey M.; Bergman, Robert G.
- Journal of the American Chemical Society, Vol. 108, Issue 7
Reversible carbon-hydrogen bond insertion/reductive elimination in (.eta.5-pentamethylcyclopentadienyl)(trimethylphosphine)iridium complexes. Use in determining relative metal-carbon bond energies and thermally activating methane
journal, February 1984
- Wax, Michael J.; Stryker, Jeffrey M.; Buchanan, J. Michael
- Journal of the American Chemical Society, Vol. 106, Issue 4
The mechanism and thermodynamics of alkane and arene carbon-hydrogen bond activation in (C5Me5)Rh(PMe3)(R)H
journal, March 1984
- Jones, William D.; Feher, Frank J.
- Journal of the American Chemical Society, Vol. 106, Issue 6
Comparative reactivities of hydrocarbon carbon-hydrogen bonds with a transition-metal complex
journal, March 1989
- Jones, William D.; Feher, Frank J.
- Accounts of Chemical Research, Vol. 22, Issue 3
Heats of reaction of Cp(PMe3)Ir(R)(H) (R = C6H5, C6H11, H) with HCl, CCl4, CBr4, and MeI. A solution thermochemical study of the C-H insertion reaction
journal, May 1987
- Nolan, S. P.; Hoff, C. D.; Stoutland, P. O.
- Journal of the American Chemical Society, Vol. 109, Issue 10
Activation of carbonhydrogen bonds by metal complexes: Mechanistic, kinetic and thermodynamic considerations
journal, May 1985
- Halpern, Jack
- Inorganica Chimica Acta, Vol. 100, Issue 1
Gas-Phase Rates of Alkane C-H Oxidative Addition to a Transient CpRh(CO) Complex
journal, January 1992
- Wasserman, E. P.; Moore, C. B.; Bergman, R. G.
- Science, Vol. 255, Issue 5042
Transition metal-hydrogen and metal-carbon bond strengths: the keys to catalysis
journal, June 1990
- Simoes, J. A. Martinho; Beauchamp, J. L.
- Chemical Reviews, Vol. 90, Issue 4
Hydrocarbon Activation via Reversible 1,2-RH-Elimination from ( t Bu 3 SiNH) 3 ZrR: Synthetic, Structural, and Mechanistic Investigations
journal, January 1996
- Schaller, Christopher P.; Cummins, Christopher C.; Wolczanski, Peter T.
- Journal of the American Chemical Society, Vol. 118, Issue 3
Photolysis of Tp'Rh(CN-neopentyl)(.eta.2-PhN:C:N-neopentyl) in alkanes and arenes: kinetic and thermodynamic selectivity of [Tp'Rh(CN-neopentyl)] for various types of carbon-hydrogen bonds
journal, January 1993
- Jones, William D.; Hessell, Edward T.
- Journal of the American Chemical Society, Vol. 115, Issue 2
Selectivities in Hydrocarbon Activation: Kinetic and Thermodynamic Investigations of Reversible 1,2-RH-Elimination from (silox) 2 ( t Bu 3 SiNH)TiR (silox = t Bu 3 SiO)
journal, November 1997
- Bennett, Jordan L.; Wolczanski, Peter T.
- Journal of the American Chemical Society, Vol. 119, Issue 44
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
- Schaller, Christopher P.; Wolczanski, Peter T.
- Inorganic Chemistry, Vol. 32, Issue 2
Relative bond dissociation energies for early transition metal alkyl, aryl, alkynyl and hydride compounds. Equilibration of metallated cyclopentadienyl derivatives of peralkylated hafnocene and scandocene with hydrocarbons and dihydrogen
journal, January 1988
- Bulls, A. Ray; Bercaw, John E.; Manriquez, Juan M.
- Polyhedron, Vol. 7, Issue 16-17
Relative metal-hydrogen, -oxygen, -nitrogen, and -carbon bond strengths for organoruthenium and organoplatinum compounds; equilibrium studies of Cp*(PMe3)2RuX and (DPPE)MePtX systems
journal, March 1987
- Bryndza, Henry E.; Fong, Lawrence K.; Paciello, Rocco A.
- Journal of the American Chemical Society, Vol. 109, Issue 5
Organometallic thermochemistry. Metal hydrocarbyl, hydride, halide, carbonyl, amide, and alkoxide bond enthalpy relationships and their implications in pentamethylcyclopentadienyl and cyclopentadienyl complexes of zirconium and hafnium
journal, November 1988
- Schock, Laurel E.; Marks, Tobin J.
- Journal of the American Chemical Society, Vol. 110, Issue 23
Validation of the M−C/H−C Bond Enthalpy Relationship through Application of Density Functional Theory
journal, June 2006
- Clot, Eric; Mégret, Claire; Eisenstein, Odile
- Journal of the American Chemical Society, Vol. 128, Issue 25
Bond energy M–C/H–C correlations: dual theoretical and experimental approach to the sensitivity of M–C bond strength to substituentsElectronic supplementary information (ESI) available: methods of calculation; Fig. S1: Comparison of calculated and experimental C–H bond dissociation energies for organic molecules; Table S1, comparison of calculated and experimental CO-stretching frequencies; Table S2, total energies, BDE for Re–C and H–C; Table S3, NPA charges q(C) and q(aryl) for the organic fragments C6H6–nFn and the rhenium complexes; preparation and spectroscopic data for Re(η5-C5Me5)(CO)2(2,6-C6H3F2)H. See http://www.rsc.org/suppdata/cc/b2/b210036n/
journal, January 2003
- Clot, Eric; Besora, Maria; Maseras, Feliu
- Chemical Communications, Issue 4
cis–trans Isomerisation of CpRe(CO) 2 (H)(Ar F ) (Ar F = C 6 F n H 5−n ; n = 0–5) is the rate determining step in C–H activation of fluoroarenes: a DFT study
journal, January 2003
- Clot, Eric; Oelckers, Beatriz; Klahn, A. Hugo
- Dalton Trans., Issue 21
Exceptional Sensitivity of Metal−Aryl Bond Energies to ortho -Fluorine Substituents: Influence of the Metal, the Coordination Sphere, and the Spectator Ligands on M−C/H−C Bond Energy Correlations
journal, June 2009
- Clot, Eric; Mégret, Claire; Eisenstein, Odile
- Journal of the American Chemical Society, Vol. 131, Issue 22
Computational Studies of Metal−Ligand Bond Enthalpies across the Transition Metal Series
journal, November 2006
- Uddin, Jamal; Morales, Christine M.; Maynard, James H.
- Organometallics, Vol. 25, Issue 23
Carbon–hydrogen bond activation of chloroalkanes by a rhodium trispyrazolylborate complex
journal, January 2004
- Vetter, Andrew J.; Jones, William D.
- Polyhedron, Vol. 23, Issue 2-3
Selective C−H Activation of Haloalkanes using a Rhodiumtrispyrazolylborate Complex
journal, August 2009
- Vetter, Andrew J.; Rieth, Ryan D.; Brennessel, William W.
- Journal of the American Chemical Society, Vol. 131, Issue 30
The activation of alkyl cyanides using a rhodiumtrispyrazolylborate complex
journal, March 2007
- Vetter, A. J.; Rieth, R. D.; Jones, W. D.
- Proceedings of the National Academy of Sciences, Vol. 104, Issue 17
Rhodium–Carbon Bond Energies in Tp′Rh(CNneopentyl)(CH 2 X)H: Quantifying Stabilization Effects in M–C Bonds
journal, April 2013
- Jiao, Yunzhe; Evans, Meagan E.; Morris, James
- Journal of the American Chemical Society, Vol. 135, Issue 18
Mechanism of benzene loss from Tp'Rh(H)(Ph)(CN-neopentyl) in the presence of neopentyl isocyanide. Evidence for an associatively induced reductive elimination
journal, July 1992
- Jones, William D.; Hessell, Edward T.
- Journal of the American Chemical Society, Vol. 114, Issue 15
Carbon−Hydrogen and Carbon−Carbon Bond Activation of Cyclopropane by a Hydridotris(pyrazolyl)borate Rhodium Complex
journal, September 1998
- Wick, Douglas D.; Northcutt, Todd O.; Lachicotte, Rene J.
- Organometallics, Vol. 17, Issue 20
Kinetic and Thermodynamic Selectivity of Intermolecular C–H Activation at [Tp′Rh(PMe 3 )]. How Does the Ancillary Ligand Affect the Metal–Carbon Bond Strength?
journal, October 2013
- Jiao, Yunzhe; Morris, James; Brennessel, William W.
- Journal of the American Chemical Society, Vol. 135, Issue 43
Synthesis and energetics of Tp′Rh[P(OMe) 3 ](R)H: a systematic investigation of ligand effects on C–H activation at rhodium
journal, January 2014
- Jiao, Yunzhe; Brennessel, William W.; Jones, William D.
- Chem. Sci., Vol. 5, Issue 2
Regio- and Stereoselective Monoamination of Diketones without Protecting Groups
journal, May 2012
- Simon, Robert C.; Grischek, Barbara; Zepeck, Ferdinand
- Angewandte Chemie International Edition, Vol. 51, Issue 27
Synthesis and structure of rhodium complexes containing a photolabile .eta.2-carbodiimide ligand. 1,3-Dipolar cycloaddition of phenyl azide to Tp'Rh(CNR)2 [Tp' = hydrotris(3,5-dimethylpyrazolyl)borate]
journal, April 1992
- Hessell, Edward T.; Jones, William D.
- Organometallics, Vol. 11, Issue 4
Regio- and Stereoselective Monoamination of Diketones without Protecting Groups
journal, May 2012
- Simon, Robert C.; Grischek, Barbara; Zepeck, Ferdinand
- Angewandte Chemie, Vol. 124, Issue 27