ACS Publications. Most Trusted. Most Cited. Most Read

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Am. Chem. Soc. 2014, 136, 24, 8614-8625
RETURN TO ISSUEPREVArticleNEXT

Carbon–Hydrogen Activation of Cycloalkanes by Cyclopentadienylcarbonylrhodium—A Lifetime Enigma

View Author Information
† Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States
‡ School of Chemistry, University of Nottingham, University Park NG7 2RD, U.K.
§ Science Program, Texas A&M University at Qatar, Doha, Qatar
⊥ Department of Chemistry, University of Belgrade, 11000 Belgrade, Serbia
[email protected]
[email protected]
Cite this: J. Am. Chem. Soc. 2014, 136, 24, 8614–8625
Publication Date (Web):May 13, 2014
https://doi.org/10.1021/ja5014773
Copyright © 2014 American Chemical Society
RIGHTS & PERMISSIONS

Article Views

2044

Altmetric

-

Citations

29
LEARN ABOUT THESE METRICS
Read OnlinePDF (4 MB)
Get e-Alerts
Supporting Info (1)»
SUBJECTS:

Abstract

Abstract Image

Carbon–hydrogen bond activation reactions of four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) by the Cp′Rh(CO) fragments (Cp′ = η5-C5H5 (Cp) or η5-C5Me5 (Cp*)) were modeled theoretically by combining density functional and coupled cluster theories, and their reaction rates were measured by fast time-resolved infrared spectroscopy. The reaction has two steps, starting with the formation of a σ-complex intermediate, followed by oxidative addition of the C–H bond by the rhodium. A range of σ-complex stabilities among the electronically unique C–H bonds in a cycloalkane were calculated and are related to the individual strengths of the C–H bond’s interactions with the Rh fragment and the steric repulsion that is incurred upon forming the specific σ-complex. The unexpectedly large increase in the lifetimes of the σ-complexes from cyclohexane to cycloheptane was predicted to be due to the large range of stabilities of the different σ-complexes found for cycloheptane. The reaction lifetimes were simulated with two mechanisms, with and without migrations among the different σ-complexes, to determine if ring migrations prior to C–H activation were influencing the rate. Both mechanisms predicted similar lifetimes for cyclopentane, cyclohexane, and, to a lesser extent, cycloheptane, suggesting ring migrations do not have a large impact on the rate of C–H activation for these cycloalkanes. For cyclooctane, the inclusion of ring migrations in the reaction mechanism led to a more accurate prediction of the lifetime, indicating that ring migrations did have an effect on the rate of C–H activation for this alkane, and that migration among the σ-complexes is faster than the C–H activation for this larger cycloalkane.

Supporting Information

ARTICLE SECTIONS
Jump To

Energy scaling procedures, scaled and unscaled free energy barriers for C–H activations and σ-complex migrations, and Cartesian coordinates for all 160 structures described in the text. This material is available free of charge via the Internet at http://pubs.acs.org.

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Cited By

This article is cited by 29 publications.

  1. Dragan B. Ninković, Salvador Moncho, Predrag Petrović, Michael B. Hall, Snežana D. Zarić, Edward N. Brothers. Improving a Methane C–H Activation Complex by Metal and Ligand Alterations from Computational Results. Inorganic Chemistry 2023, 62 (13) , 5058-5066. https://doi.org/10.1021/acs.inorgchem.2c03342
  2. Laurence R. Doyle, Martin R. Galpin, Samantha K. Furfari, Bengt E. Tegner, Antonio J. Martínez-Martínez, Adrian C. Whitwood, Scott A. Hicks, Guy C. Lloyd-Jones, Stuart A. Macgregor, Andrew S. Weller. Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex. Organometallics 2022, 41 (3) , 284-292. https://doi.org/10.1021/acs.organomet.1c00639
  3. Xin Yang, Michael B. Hall. Theoretical Analysis of Competing Pathways for Carbon–Hydrogen Activation of Cyclopentadienyl–Triphenylphosphine–Iridium in Benzene. Inorganic Chemistry 2019, 58 (24) , 16553-16558. https://doi.org/10.1021/acs.inorgchem.9b02580
  4. Alasdair I. McKay, Alexander J. Bukvic, Bengt E. Tegner, Arron L. Burnage, Antonio J. Martı́nez-Martı́nez, Nicholas H. Rees, Stuart A. Macgregor, Andrew S. Weller. Room Temperature Acceptorless Alkane Dehydrogenation from Molecular σ-Alkane Complexes. Journal of the American Chemical Society 2019, 141 (29) , 11700-11712. https://doi.org/10.1021/jacs.9b05577
  5. Ryan Carlsen, Jordan R. Jenkins, Tsung-Chiang Johnny Huang, Samuel L. Pugh, Daniel H. Ess. Paddle Ball Dynamics during Conversion of a Rh–Methyl Hydride Complex to a Rh–Methane σ-Complex through Reductive Coupling. Organometallics 2019, 38 (10) , 2280-2287. https://doi.org/10.1021/acs.organomet.8b00936
  6. Abhranil Biswas, Arkady Ellern, Aaron D. Sadow. CO Displacement in an Oxidative Addition of Primary Silanes to Rhodium(I). Inorganic Chemistry 2019, 58 (6) , 3815-3824. https://doi.org/10.1021/acs.inorgchem.8b03425
  7. Antonio J. Martínez-Martínez, Bengt E. Tegner, Alasdair I. McKay, Alexander J. Bukvic, Nicholas H. Rees, Graham J. Tizzard, Simon J. Coles, Mark R. Warren, Stuart A. Macgregor, Andrew S. Weller. Modulation of σ-Alkane Interactions in [Rh(L2)(alkane)]+ Solid-State Molecular Organometallic (SMOM) Systems by Variation of the Chelating Phosphine and Alkane: Access to η2,η2-σ-Alkane Rh(I), η1-σ-Alkane Rh(III) Complexes, and Alkane Encapsulation. Journal of the American Chemical Society 2018, 140 (44) , 14958-14970. https://doi.org/10.1021/jacs.8b09364
  8. Wenjing Liu, Jia Zheng, Zheyuan Liu, Wenping Hu, Xiaotai Wang, Yanfeng Dang. How Does Palladium–Amino Acid Cooperative Catalysis Enable Regio- and Stereoselective C(sp3)–H Functionalization in Aldehydes and Ketones? A DFT Mechanistic Study. ACS Catalysis 2018, 8 (8) , 7698-7709. https://doi.org/10.1021/acscatal.8b02281
  9. Jia Guan, Alisdair Wriglesworth, Xue Zhong Sun, Edward N. Brothers, Snežana D. Zarić, Meagan E. Evans, William D. Jones, Michael Towrie, Michael B. Hall, and Michael W. George . Probing the Carbon–Hydrogen Activation of Alkanes Following Photolysis of Tp′Rh(CNR)(carbodiimide): A Computational and Time-Resolved Infrared Spectroscopic Study. Journal of the American Chemical Society 2018, 140 (5) , 1842-1854. https://doi.org/10.1021/jacs.7b12152
  10. Dragan B. Ninković, Salvador Moncho, Predrag V. Petrović, Snežana D. Zarić, Michael B. Hall, and Edward N. Brothers . Methane Activations by Titanium Neopentylidene Complexes: Electronic Resilience and Steric Control. Inorganic Chemistry 2017, 56 (15) , 9264-9272. https://doi.org/10.1021/acs.inorgchem.7b01340
  11. F. Mark Chadwick, Tobias Krämer, Torsten Gutmann, Nicholas H. Rees, Amber L. Thompson, Alison J. Edwards, Gerd Buntkowsky, Stuart A. Macgregor, and Andrew S. Weller . Selective C–H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange. Journal of the American Chemical Society 2016, 138 (40) , 13369-13378. https://doi.org/10.1021/jacs.6b07968
  12. Sebastian D. Pike, F. Mark Chadwick, Nicholas H. Rees, Mark P. Scott, Andrew S. Weller, Tobias Krämer, and Stuart A. Macgregor . Solid-State Synthesis and Characterization of σ-Alkane Complexes, [Rh(L2)(η2,η2-C7H12)][BArF4] (L2 = Bidentate Chelating Phosphine). Journal of the American Chemical Society 2015, 137 (2) , 820-833. https://doi.org/10.1021/ja510437p
  13. Hejing Gong, Qiong Luo, Qian-shu Li, Yaoming Xie, R. Bruce King, and Henry F. Schaefer, III . Cyclization of Thiocarbonyl Groups in Binuclear Homoleptic Nickel Thiocarbonyls To Give Ligands Derived from Sulfur Analogues of Croconic and Rhodizonic Acids. Inorganic Chemistry 2015, 54 (1) , 132-142. https://doi.org/10.1021/ic501924p
  14. Tobias Krämer, F. Mark Chadwick, Stuart A. Macgregor, Andrew S. Weller. Solid‐State Confinement Effects in Selective exo ‐H/D Exchange in the Rhodium σ‐Norbornane Complex [(Cy 2 PCH 2 CH 2 PCy 2 )Rh(η 2 :η 2 ‐C 7 H 12 )][BAr F 4 ]. Helvetica Chimica Acta 2023, 106 (2) https://doi.org/10.1002/hlca.202200154
  15. Kristof M. Altus, Jennifer A. Love. The continuum of carbon–hydrogen (C–H) activation mechanisms and terminology. Communications Chemistry 2021, 4 (1) https://doi.org/10.1038/s42004-021-00611-1
  16. Timothy M. Boyd, Bengt E. Tegner, Graham J. Tizzard, Antonio J. Martínez‐Martínez, Samuel E. Neale, Michael A. Hayward, Simon J. Coles, Stuart A. Macgregor, Andrew S. Weller. A Structurally Characterized Cobalt(I) σ‐Alkane Complex. Angewandte Chemie 2020, 132 (15) , 6236-6240. https://doi.org/10.1002/ange.201914940
  17. Timothy M. Boyd, Bengt E. Tegner, Graham J. Tizzard, Antonio J. Martínez‐Martínez, Samuel E. Neale, Michael A. Hayward, Simon J. Coles, Stuart A. Macgregor, Andrew S. Weller. A Structurally Characterized Cobalt(I) σ‐Alkane Complex. Angewandte Chemie International Edition 2020, 59 (15) , 6177-6181. https://doi.org/10.1002/anie.201914940
  18. Niels Rothermel, Donia Bouzouita, Tobias Röther, Iker de Rosal, Simon Tricard, Romuald Poteau, Torsten Gutmann, Bruno Chaudret, Hans‐Heinrich Limbach, Gerd Buntkowsky. Surprising Differences of Alkane C‐H Activation Catalyzed by Ruthenium Nanoparticles: Complex Surface‐Substrate Recognition?. ChemCatChem 2018, 10 (19) , 4243-4247. https://doi.org/10.1002/cctc.201801022
  19. Jia Guan, Snežana D Zarić, Edward N. Brothers, Michael B. Hall. Recent computational studies on transition-metal carbon-hydrogen bond activation of alkanes. International Journal of Quantum Chemistry 2018, 118 (9) , e25605. https://doi.org/10.1002/qua.25605
  20. Hans-Heinrich Limbach, Tal Pery, Niels Rothermel, Bruno Chaudret, Torsten Gutmann, Gerd Buntkowsky. Gas phase 1 H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange. Physical Chemistry Chemical Physics 2018, 20 (16) , 10697-10712. https://doi.org/10.1039/C7CP07770J
  21. Dušan P. Malenov, Ivana S. Antonijević, Michael B. Hall, Snežana D. Zarić. Stacking of cyclopentadienyl organometallic sandwich and half-sandwich compounds. Strong interactions of sandwiches at large offsets. CrystEngComm 2018, 20 (31) , 4506-4514. https://doi.org/10.1039/C8CE00597D
  22. Аlbert А. Shteinman. Activation and selective oxy-functionalization of alkanes with metal complexes: Shilov reaction and some new aspects. Journal of Molecular Catalysis A: Chemical 2017, 426 , 305-315. https://doi.org/10.1016/j.molcata.2016.08.020
  23. Arghya Banerjee, Satavisha Sarkar, Bhisma K. Patel. C–H functionalisation of cycloalkanes. Organic & Biomolecular Chemistry 2017, 15 (3) , 505-530. https://doi.org/10.1039/C6OB01975G
  24. Jie Wang, Ruoyu Sang, Xiaolong Chong, Yinuo Zhao, Wenjie Fan, Zejiang Li, Jincan Zhao. Copper-catalyzed radical cascade oxyalkylation of olefinic amides with simple alkanes: highly efficient access to benzoxazines. Chemical Communications 2017, 53 (56) , 7961-7964. https://doi.org/10.1039/C7CC04213B
  25. A.S. Weller, F.M. Chadwick, A.I. McKay. Transition Metal Alkane-Sigma Complexes. 2016, 223-276. https://doi.org/10.1016/bs.adomc.2016.09.001
  26. Murugesan Thenraj, Ashoka G. Samuelson. Contrasting electronic requirements for CH binding and CH activation in d 6 half-sandwich complexes of rhenium and tungsten. Journal of Computational Chemistry 2015, 36 (24) , 1818-1830. https://doi.org/10.1002/jcc.24002
  27. James A. Calladine, Raphael Horvath, Andrew J. Davies, Alisdair Wriglesworth, Xue-Zhong Sun, Michael W. George. Probing Organometallic Reactions by Time-Resolved Infrared Spectroscopy in Solution and in the Solid State Using Quantum Cascade Lasers. Applied Spectroscopy 2015, 69 (5) , 519-524. https://doi.org/10.1366/14-07708
  28. Magnus W. D. Hanson-Heine, Alisdair Wriglesworth, Maliha Uroos, James A. Calladine, Thomas S. Murphy, Michelle Hamilton, Ian P. Clark, Michael Towrie, James Dowden, Nicholas A. Besley, Michael W. George. Calculating singlet excited states: Comparison with fast time-resolved infrared spectroscopy of coumarins. The Journal of Chemical Physics 2015, 142 (15) , 154119. https://doi.org/10.1063/1.4917311
  29. Yan-Yan Guo, Wei-Jie Chi, Ze-Sheng Li, Quan-Song Li. Molecular design of N–NO 2 substituted cycloalkanes derivatives C m (N–NO 2 ) m for energetic materials with high detonation performance and low impact sensitivity. RSC Advances 2015, 5 (48) , 38048-38055. https://doi.org/10.1039/C5RA04509F

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect