C–H and O 2 Activation at a Pt(II) Center Enabled by a Novel Sulfonated CNN Pincer Ligand

Watts, David; Wang, Daoyong; Adelberg, Mackenzie; Zavalij, Peter Y.; Vedernikov, Andrei N.

doi:10.1021/acs.organomet.6b00613

Title: C–H and O ₂ Activation at a Pt(II) Center Enabled by a Novel Sulfonated CNN Pincer Ligand

Abstract

A novel sulfonated CNN pincer ligand has been designed to support CH and O₂ activation at a Pt(II) center. The derived cycloplatinated aqua complex 7 was found to be one of the most active reported homogeneous Pt catalysts for H/D exchange between studied arenes (benzene, benzene-d₆, toluene-d₈, p-xylene, and mesitylene) and 2,2,2-trifluoroethanol (TFE) or 2,2,2-trifluoroethanol-d; the TON for C₆D₆ as a substrate is >250 after 48 h at 80 °C. The reaction is very selective; no benzylic CH bond activation was observed. The per-CH-bond reactivity diminishes in the series benzene (19) > toluene (p-CH:m-CH:o-CH = 1:0.9:0.2) > xylene (2.9) > mesitylene (1.1). The complex 7 reacts slowly in TFE solutions under ambient light but not in the dark with O₂ to selectively produce a Pt(IV) trifluoroethoxo derivative. The H/D exchange reaction kinetics and results of the DFT study suggest that complex 7, and not its TFE derivatives, is the major species responsible for the arene CH bond activation. Lastly, the reaction deuterium kinetic isotope effect, k_H/k_D = 1.7, the reaction selectivity, and reaction kinetics modeling suggest that the CH bond cleavage step is rate-determining.

Authors:

Watts, David ^[1]; Wang, Daoyong ^[1]; Adelberg, Mackenzie ^[1]; Zavalij, Peter Y. ^[1]; Vedernikov, Andrei N. ^[1]

Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States

Publication Date:: Wed Sep 21 00:00:00 EDT 2016

Research Org.:: Univ. of Maryland, College Park, MD (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Catalytic Hydrocarbon Functionalization (CCHF)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1325840

Alternate Identifier(s):: OSTI ID: 1339955

Grant/Contract Number:: SC0001298

Resource Type:: Published Article

Journal Name:: Organometallics

Additional Journal Information:: Journal Name: Organometallics Journal Volume: 36 Journal Issue: 1; Journal ID: ISSN 0276-7333

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Watts, David, Wang, Daoyong, Adelberg, Mackenzie, Zavalij, Peter Y., and Vedernikov, Andrei N. C–H and O 2 Activation at a Pt(II) Center Enabled by a Novel Sulfonated CNN Pincer Ligand.  United States: N. p., 2016. 
Web.  doi:10.1021/acs.organomet.6b00613.

Copy to clipboard


                    Watts, David, Wang, Daoyong, Adelberg, Mackenzie, Zavalij, Peter Y., & Vedernikov, Andrei N. C–H and O 2 Activation at a Pt(II) Center Enabled by a Novel Sulfonated CNN Pincer Ligand.  United States.  https://doi.org/10.1021/acs.organomet.6b00613

Copy to clipboard


                    Watts, David, Wang, Daoyong, Adelberg, Mackenzie, Zavalij, Peter Y., and Vedernikov, Andrei N. Wed .  
"C–H and O 2 Activation at a Pt(II) Center Enabled by a Novel Sulfonated CNN Pincer Ligand".  United States.  https://doi.org/10.1021/acs.organomet.6b00613.

Copy to clipboard


                    
@article{osti_1325840,

  title        = {C–H and O 2 Activation at a Pt(II) Center Enabled by a Novel Sulfonated CNN Pincer Ligand},

  author       = {Watts, David and Wang, Daoyong and Adelberg, Mackenzie and Zavalij, Peter Y. and Vedernikov, Andrei N.},

  abstractNote = {A novel sulfonated CNN pincer ligand has been designed to support CH and O2 activation at a Pt(II) center. The derived cycloplatinated aqua complex 7 was found to be one of the most active reported homogeneous Pt catalysts for H/D exchange between studied arenes (benzene, benzene-d6, toluene-d8, p-xylene, and mesitylene) and 2,2,2-trifluoroethanol (TFE) or 2,2,2-trifluoroethanol-d; the TON for C6D6 as a substrate is >250 after 48 h at 80 °C. The reaction is very selective; no benzylic CH bond activation was observed. The per-CH-bond reactivity diminishes in the series benzene (19) > toluene (p-CH:m-CH:o-CH = 1:0.9:0.2) > xylene (2.9) > mesitylene (1.1). The complex 7 reacts slowly in TFE solutions under ambient light but not in the dark with O2 to selectively produce a Pt(IV) trifluoroethoxo derivative. The H/D exchange reaction kinetics and results of the DFT study suggest that complex 7, and not its TFE derivatives, is the major species responsible for the arene CH bond activation. Lastly, the reaction deuterium kinetic isotope effect, kH/kD = 1.7, the reaction selectivity, and reaction kinetics modeling suggest that the CH bond cleavage step is rate-determining.},

  doi          = {10.1021/acs.organomet.6b00613},

  journal      = {Organometallics},

  number       = 1,

  volume       = 36,

  place        = {United States},

  year         = {Wed Sep 21 00:00:00 EDT 2016},

  month        = {Wed Sep 21 00:00:00 EDT 2016}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1021/acs.organomet.6b00613

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 15 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

CCDC 1527900: Experimental Crystal Structure Determination: RAKXAF : catena-[(μ-2-{6-[(pyridin-2-yl)(sulfonato)methyl]pyridin-2-yl}phenyl)-chloro-(μ-methanol)-(μ-aqua)-aqua-platinum-potassium]
dataset, January 2017

Watts, David; Wang, Daoyong; Adelberg, Mackenzie
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1n8x3y

CCDC 1527901: Experimental Crystal Structure Determination: RAKXEJ : aqua-(2-{6-[(pyridin-2-yl)(sulfonato)methyl]pyridin-2-yl}phenyl)-platinum(ii) tetrahydrate
dataset, January 2017

Watts, David; Wang, Daoyong; Adelberg, Mackenzie
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1n8x4z

CCDC 1527902: Experimental Crystal Structure Determination: RAKXIN : (2-{6-[(pyridin-2-yl)(sulfonato)methyl]pyridin-2-yl}phenyl)-(2,2,2-trifluoroethan-1-olato)-hydroxo-platinum(iv) 2,2,2-trifluoroethan-1-ol diethyl ether solvate
dataset, January 2017

Watts, David; Wang, Daoyong; Adelberg, Mackenzie
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1n8x50

Phosphine-Free Bis(Pyrrolyl)pyridine Based NNN-Pincer Palladium(II) Complexes as Efficient Catalysts for Suzuki-Miyaura Cross-Coupling Reactions of Aryl Bromides in Aqueous Medium
journal, August 2018

Yadav, Seema; Singh, Ajeet; Rashid, Nusrat
ChemistrySelect, Vol. 3, Issue 32
DOI: 10.1002/slct.201801647

Preparation and characterization of terdentate [C,N,N] acetophenone and acetylpyridine hydrazone platinacycles: a DFT insight into the reaction mechanism
journal, January 2017

Marcos, Ismael; Ojea, Vicente; Vázquez-García, Digna
Dalton Transactions, Vol. 46, Issue 48
DOI: 10.1039/c7dt03418k

Phosphine-Free Bis(Pyrrolyl)pyridine Based NNN-Pincer Palladium(II) Complexes as Efficient Catalysts for Suzuki-Miyaura Cross-Coupling Reactions of Aryl Bromides in Aqueous Medium
journal, August 2018

Yadav, Seema; Singh, Ajeet; Rashid, Nusrat
ChemistrySelect, Vol. 3, Issue 32
DOI: 10.1002/slct.201801647

Preparation and characterization of terdentate [C,N,N] acetophenone and acetylpyridine hydrazone platinacycles: a DFT insight into the reaction mechanism
journal, January 2017

Marcos, Ismael; Ojea, Vicente; Vázquez-García, Digna
Dalton Transactions, Vol. 46, Issue 48
DOI: 10.1039/c7dt03418k

Novel Sulfonated CNN Pincer Ligands for Facile C−H Activation at a Pt(II) Center
journal, October 2017

Watts, David; Wang, Daoyong; Zavalij, Peter Y.
Israel Journal of Chemistry, Vol. 57, Issue 10-11
DOI: 10.1002/ijch.201700063

Similar Records in DOE PAGES and OSTI.GOV collections:

Mechanism and thermodynamics of alkane and arene carbon-hydrogen bond activation in (C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)(R)H

Journal Article Jones, W D ; Feher, F J - J. Am. Chem. Soc.; (United States)

The complexes (C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)(R)X(R=Me(CH/sub 3/),Ph-)Phenyl), p-tolyl,3,4-C/sub 6/H/sub 3/Me/sub 2/, 2,5-C6H/sub 3/Me2, and C=CH=CHgreater than or equal to-CH/sub 2/-CH/sub 2/;X=Br) react with hydride doners Li(HB(sec-Bu/sub 3/ (butyl)) or Na/sup +/(H/sub 2/Al(OCH/sub 2/CH/sub 2/CH/sub 2/OCH/sub 3/)/sub 2/)-to produce (C/sub 5/Me5)Rh(PMe/sub 3/)(R)H. The complexes with R=alkyl or R=vinyl are unstable, undergoing rapid reductive elimination at 25/sup 0/C, but can be observed by /sub 1/H NMR below -20/sup 0/C. (C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)(CH/sub 3/)H undergoes first-order reductive elimination with k=(6.38 +/-0.10) X 10/sup -5/ s/sup -1/ at -17/sup 0/C. In contrast, (c/sub 5/Me/sub 5/)Rh(PMe/sub 3/)(C/sub 6/H/sub 5/)h undergoes a more complicated first-ordermore »« less
https://doi.org/10.1021/ja00318a018
Novel Sulfonated CNN Pincer Ligands for Facile C−H Activation at a Pt(II) Center

Journal Article Watts, David ; Wang, Daoyong ; Zavalij, Peter Y. ; ... - Israel Journal of Chemistry

Abstract Two novel sulfonated CNN‐pincer ligands 1b and 1c and the corresponding chloro and aqua complexes K[ ^CNN LPtCl] and ^CNN LPt(H ₂ O), 3b – 3c and 2b – 2c , were prepared and fully characterized including single crystal X‐ray diffraction. Along with the previously described complexes 2a and 3a , the derivatives of a CNN pincer ligand 1a , these complexes form a family of structurally similar compounds where the pincer core rigidity increases in the series 2a (3a) < 2b (3b) < 2c ( 3c ), as deduced from their XRD data. The increased ligand rigidity affectsmore »« less
Cited by 4
https://doi.org/10.1002/ijch.201700063
Supported organoactinide complexes as heterogeneous catalysts. A kinetic and mechanistic study of facile arene hydrogenation

Journal Article Eisen, M S ; Marks, T J - Journal of the American Chemical Society; (United States)

This contribution reports a kinetic and mechanistic study of arene hydrogenation by the supported organoactinide complexes Cp[prime]Th(benzyl)[sub 3]/DA (1/DA), Th(1,3,5-CH[sub 2]C[sub 6]H[sub 3]Me[sub 2])[sub 4]/DA (2/DA), and Th([eta][sup 3]-allyl)[sub 4]/DA (3/DA) where Cp[prime] = [eta][sup 5]-Me[sub 5]C[sub 5] and DA = dehydroxylated [gamma]-alumina. In slurry reactions (90[degrees]C, P[sub H[sub 2]] = 180 psi), the activity for benzene hydrogenation follows the order 1/DA < 2/DA < 3/DA with an N[sub t] value for 3/DA of [approximately]25,000 h[sup [minus]1] active site[sup [minus]1]. This approaches or exceeds most conventional platinum metal catalysts in efficacy for benzene reduction. Partially hydrogenation products cannot be detectedmore »« less
https://doi.org/10.1021/ja00052a036
An investigation of the photochemical properties of transition metal arene complexes: Final report for the period July 1, 1983 to June 30, 1987

Technical Report Mann, K R

The photochemical removal of the arene from CpM(eta/sup 6/-arene)/sup +/ was studied for complexes of Fe(II) and Ru(II); (Fe, arene = p-dichlorobenzene, benzene, toluene, d/sub 8/-toluene, p-xylene, mesitylene, durene, pentamethylbenzene, hexamethylbenzene, hexaethylbenzene, and tri-t-butylbenzene; Ru, p-dichlorobenzene, benzene, toluene, mesitylene, pentamethylbenzene, hexamethylbenzene, and tri-t-butylbenzene). Quantum yields were determined. The photoactive state was identified as the distorted a/sup 3/E/sub 1/ ligand field excited state. The excited state energy of the Fe complexes lies about 14,000 cm/sup -1/ above ground state. A theoretical photophysical model was developed to relate the quantum yield for arene release to the rate of arene release. This modelmore »« less
Isotope effects in arene C-H bond activation by ((C/sub 5/Me/sub 5/)Rh(PMe/sub 3/))

Journal Article Jones, W D ; Feher, F J - J. Am. Chem. Soc.; (United States)

The isotope effects involved in the activation of arene C-H bonds by the intermediate ((C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)) have been investigated. The ratio k/sub H/k/sub D/ for coordination to a double bond in benzene (the rate-determining step of arene activation) is found to be 1.05 (6), whereas k/sub H//k/sub D/ = 1.4 for the second step in which the C-H bond of the coordinated arene undergoes oxidative addition. The isotope effect K/sub H/D/ for the equilibrium between the more stable phenyl hydride complex (C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)(C/sub 6/D/sub 5/)H and the complex containing hydrogen in the ortho position of themore »« less

Other research related to this record:

Similar Records
Related Works
dataset (3)

Title: C–H and O 2 Activation at a Pt(II) Center Enabled by a Novel Sulfonated CNN Pincer Ligand

Abstract

Citation Formats

CCDC 1527900: Experimental Crystal Structure Determination: RAKXAF : catena-[(μ-2-{6-[(pyridin-2-yl)(sulfonato)methyl]pyridin-2-yl}phenyl)-chloro-(μ-methanol)-(μ-aqua)-aqua-platinum-potassium] dataset, January 2017

CCDC 1527901: Experimental Crystal Structure Determination: RAKXEJ : aqua-(2-{6-[(pyridin-2-yl)(sulfonato)methyl]pyridin-2-yl}phenyl)-platinum(ii) tetrahydrate dataset, January 2017

CCDC 1527902: Experimental Crystal Structure Determination: RAKXIN : (2-{6-[(pyridin-2-yl)(sulfonato)methyl]pyridin-2-yl}phenyl)-(2,2,2-trifluoroethan-1-olato)-hydroxo-platinum(iv) 2,2,2-trifluoroethan-1-ol diethyl ether solvate dataset, January 2017

Phosphine-Free Bis(Pyrrolyl)pyridine Based NNN-Pincer Palladium(II) Complexes as Efficient Catalysts for Suzuki-Miyaura Cross-Coupling Reactions of Aryl Bromides in Aqueous Medium journal, August 2018

Preparation and characterization of terdentate [C,N,N] acetophenone and acetylpyridine hydrazone platinacycles: a DFT insight into the reaction mechanism journal, January 2017

Phosphine-Free Bis(Pyrrolyl)pyridine Based NNN-Pincer Palladium(II) Complexes as Efficient Catalysts for Suzuki-Miyaura Cross-Coupling Reactions of Aryl Bromides in Aqueous Medium journal, August 2018

Preparation and characterization of terdentate [C,N,N] acetophenone and acetylpyridine hydrazone platinacycles: a DFT insight into the reaction mechanism journal, January 2017

Novel Sulfonated CNN Pincer Ligands for Facile C−H Activation at a Pt(II) Center journal, October 2017

Title: C–H and O ₂ Activation at a Pt(II) Center Enabled by a Novel Sulfonated CNN Pincer Ligand

CCDC 1527900: Experimental Crystal Structure Determination: RAKXAF : catena-[(μ-2-{6-[(pyridin-2-yl)(sulfonato)methyl]pyridin-2-yl}phenyl)-chloro-(μ-methanol)-(μ-aqua)-aqua-platinum-potassium]
dataset, January 2017

CCDC 1527901: Experimental Crystal Structure Determination: RAKXEJ : aqua-(2-{6-[(pyridin-2-yl)(sulfonato)methyl]pyridin-2-yl}phenyl)-platinum(ii) tetrahydrate
dataset, January 2017

CCDC 1527902: Experimental Crystal Structure Determination: RAKXIN : (2-{6-[(pyridin-2-yl)(sulfonato)methyl]pyridin-2-yl}phenyl)-(2,2,2-trifluoroethan-1-olato)-hydroxo-platinum(iv) 2,2,2-trifluoroethan-1-ol diethyl ether solvate
dataset, January 2017

Phosphine-Free Bis(Pyrrolyl)pyridine Based NNN-Pincer Palladium(II) Complexes as Efficient Catalysts for Suzuki-Miyaura Cross-Coupling Reactions of Aryl Bromides in Aqueous Medium
journal, August 2018

Preparation and characterization of terdentate [C,N,N] acetophenone and acetylpyridine hydrazone platinacycles: a DFT insight into the reaction mechanism
journal, January 2017

Phosphine-Free Bis(Pyrrolyl)pyridine Based NNN-Pincer Palladium(II) Complexes as Efficient Catalysts for Suzuki-Miyaura Cross-Coupling Reactions of Aryl Bromides in Aqueous Medium
journal, August 2018

Preparation and characterization of terdentate [C,N,N] acetophenone and acetylpyridine hydrazone platinacycles: a DFT insight into the reaction mechanism
journal, January 2017

Novel Sulfonated CNN Pincer Ligands for Facile C−H Activation at a Pt(II) Center
journal, October 2017