Journal of the American Chemical Society, volume 129, issue 6, pages 1698-1704
Mechanistic Studies on 14-Electron Ruthenacyclobutanes: Degenerate Exchange with Free Ethylene
1
Contribution from the University of Calgary, 2500 University Drive N.W., Calgary, Alberta, Canada T2N 1N4
|
Publication type: Journal Article
Publication date: 2007-01-23
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 15
ISSN: 00027863, 15205126
General Chemistry
Catalysis
Biochemistry
Colloid and Surface Chemistry
Abstract
The phosphonium alkylidene [(NHC)Cl2Ru=CH(PCy3)]+[B(C6F5)4]-, 1, (NHC = N-heterocyclic carbene, Cy = cyclohexyl, C6H11) reacts with 2.2 equiv of ethylene at -50 degrees C to form the 14-electron ruthenacyclobutane (NHC)Cl2Ru(CH2CH2CH2), 2. NMR spectroscopic data indicates that 2 has a C2v symmetric structure with a flat, kite shaped ruthenacyclobutane ring with significant Calpha-Cbeta agostic interactions with the Ru center. Intramolecular exchange of Calpha and Cbeta is fast (14(2) s-1 at 223 K) as measured by EXSY spectroscopy. Intermolecular exchange of Calpha and Cbeta with the methylene groups of free ethylene is much slower and first order in both [Ru] and [H2C=CH2] (4.8(3) x 10-4 M-1 s-1). Activation parameters for this process are DeltaH++ = 13.2(5) kcal mol-1 and DeltaS++ = -15(2) cal mol-1 K-1, also consistent with a rate limiting associative substitution as the key step in this exchange process. On the basis of this observation, mechanisms for the intermolecular exchange process are proposed and the implications for the mechanism of the propagation steps in catalytic olefin metathesis as mediated by Grubbs catalysts are discussed.
Top-30
Citations by journals
|
5
10
15
20
25
|
|
|
Journal of the American Chemical Society
21 publications, 15.79%
|
|
|
Organometallics
20 publications, 15.04%
|
|
|
Chemistry - A European Journal
9 publications, 6.77%
|
|
|
ACS Catalysis
9 publications, 6.77%
|
|
|
European Journal of Inorganic Chemistry
4 publications, 3.01%
|
|
|
Angewandte Chemie - International Edition
4 publications, 3.01%
|
|
|
Angewandte Chemie
4 publications, 3.01%
|
|
|
Dalton Transactions
3 publications, 2.26%
|
|
|
Chemical Communications
3 publications, 2.26%
|
|
|
Beilstein Journal of Organic Chemistry
2 publications, 1.5%
|
|
|
Coordination Chemistry Reviews
2 publications, 1.5%
|
|
|
Journal of Organometallic Chemistry
2 publications, 1.5%
|
|
|
Journal of Organic Chemistry
2 publications, 1.5%
|
|
|
Accounts of Chemical Research
2 publications, 1.5%
|
|
|
Catalysis Science and Technology
2 publications, 1.5%
|
|
|
Chemical Society Reviews
2 publications, 1.5%
|
|
|
Catalysts
1 publication, 0.75%
|
|
|
Nature Chemistry
1 publication, 0.75%
|
|
|
Chemistry of Heterocyclic Compounds
1 publication, 0.75%
|
|
|
Theoretical Chemistry Accounts
1 publication, 0.75%
|
|
|
Tetrahedron
1 publication, 0.75%
|
|
|
Molecular Catalysis
1 publication, 0.75%
|
|
|
Polyhedron
1 publication, 0.75%
|
|
|
Journal of Computational Chemistry
1 publication, 0.75%
|
|
|
ChemSusChem
1 publication, 0.75%
|
|
|
Helvetica Chimica Acta
1 publication, 0.75%
|
|
|
Zeitschrift fur Anorganische und Allgemeine Chemie
1 publication, 0.75%
|
|
|
Advanced Synthesis and Catalysis
1 publication, 0.75%
|
|
|
Chemical Reviews
1 publication, 0.75%
|
|
|
5
10
15
20
25
|
Citations by publishers
|
10
20
30
40
50
60
|
|
|
American Chemical Society (ACS)
60 publications, 45.11%
|
|
|
Wiley
37 publications, 27.82%
|
|
|
Royal Society of Chemistry (RSC)
14 publications, 10.53%
|
|
|
Elsevier
11 publications, 8.27%
|
|
|
Springer Nature
4 publications, 3.01%
|
|
|
Beilstein-Institut
2 publications, 1.5%
|
|
|
Multidisciplinary Digital Publishing Institute (MDPI)
1 publication, 0.75%
|
|
|
Proceedings of the National Academy of Sciences (PNAS)
1 publication, 0.75%
|
|
|
Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii
1 publication, 0.75%
|
|
|
10
20
30
40
50
60
|
- We do not take into account publications without a DOI.
- Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
- Statistics recalculated weekly.
{"yearsCitations":{"type":"bar","data":{"show":true,"labels":[2007,2008,2009,2010,2011,2012,2013,2014,2015,2016,2017,2018,2019,2020,2021,2022,2023,2024],"ids":[0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0],"codes":[0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0],"imageUrls":["","","","","","","","","","","","","","","","","",""],"datasets":[{"label":"Citations number","data":[8,11,12,6,11,9,9,13,7,9,6,6,4,9,9,1,1,2],"backgroundColor":["#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6"],"percentage":["6.02","8.27","9.02","4.51","8.27","6.77","6.77","9.77","5.26","6.77","4.51","4.51","3.01","6.77","6.77","0.75","0.75","1.5"],"barThickness":null}]},"options":{"indexAxis":"x","maintainAspectRatio":true,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"},"stacked":false},"x":{"ticks":{"stepSize":1,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"},"stacked":false}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Citations per year","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}},"journals":{"type":"bar","data":{"show":true,"labels":["Journal of the American Chemical Society","Organometallics","Chemistry - A European Journal","ACS Catalysis","European Journal of Inorganic Chemistry","Angewandte Chemie - International Edition","Angewandte Chemie","Dalton Transactions","Chemical Communications","Beilstein Journal of Organic Chemistry","Coordination Chemistry Reviews","Journal of Organometallic Chemistry","Journal of Organic Chemistry","Accounts of Chemical Research","Catalysis Science and Technology","Chemical Society Reviews","Catalysts","Nature Chemistry","Chemistry of Heterocyclic Compounds","Theoretical Chemistry Accounts","Tetrahedron","Molecular Catalysis","Polyhedron","Journal of Computational Chemistry","ChemSusChem","Helvetica Chimica Acta","Zeitschrift fur Anorganische und Allgemeine Chemie","Advanced Synthesis and Catalysis","Chemical Reviews"],"ids":[4813,1409,24708,4873,15359,19215,25450,8473,9073,21928,13437,11834,8697,1526,2605,20586,3739,17228,16828,19212,3439,4906,21269,423,6896,32,18677,3906,13718],"codes":[0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0],"imageUrls":["\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/leiAYcRDGTSl5B1eCnwpSGqmDEUEfDPPoYisFGhT_medium.webp","\/storage\/images\/resized\/leiAYcRDGTSl5B1eCnwpSGqmDEUEfDPPoYisFGhT_medium.webp","\/storage\/images\/resized\/ex6KJoZujZOZFZh7jGfeHauiftuB3CI7iwJVFRDg_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/leiAYcRDGTSl5B1eCnwpSGqmDEUEfDPPoYisFGhT_medium.webp","\/storage\/images\/resized\/leiAYcRDGTSl5B1eCnwpSGqmDEUEfDPPoYisFGhT_medium.webp","\/storage\/images\/resized\/MjH1ITP7lMYGxeqUZfkt2BnVLgjkk413jwBV97XX_medium.webp","\/storage\/images\/resized\/voXLqlsvTwv5p3iMQ8Dhs95nqB4AXOG7Taj7G4ra_medium.webp","\/storage\/images\/resized\/voXLqlsvTwv5p3iMQ8Dhs95nqB4AXOG7Taj7G4ra_medium.webp","\/storage\/images\/resized\/voXLqlsvTwv5p3iMQ8Dhs95nqB4AXOG7Taj7G4ra_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp"],"datasets":[{"label":"","data":[21,20,9,9,4,4,4,3,3,2,2,2,2,2,2,2,1,1,1,1,1,1,1,1,1,1,1,1,1],"backgroundColor":["#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6"],"percentage":[15.79,15.04,6.77,6.77,3.01,3.01,3.01,2.26,2.26,1.5,1.5,1.5,1.5,1.5,1.5,1.5,0.75,0.75,0.75,0.75,0.75,0.75,0.75,0.75,0.75,0.75,0.75,0.75,0.75],"barThickness":13}]},"options":{"indexAxis":"y","maintainAspectRatio":false,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"},"stacked":false},"x":{"ticks":{"stepSize":null,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"},"stacked":false}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Journals","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}},"publishers":{"type":"bar","data":{"show":true,"labels":["American Chemical Society (ACS)","Wiley","Royal Society of Chemistry (RSC)","Elsevier","Springer Nature","Beilstein-Institut","Multidisciplinary Digital Publishing Institute (MDPI)","Proceedings of the National Academy of Sciences (PNAS)","Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii"],"ids":[40,11,123,17,8,6139,202,162,9422],"codes":[0,0,0,0,0,0,0,0,0],"imageUrls":["\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/leiAYcRDGTSl5B1eCnwpSGqmDEUEfDPPoYisFGhT_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/voXLqlsvTwv5p3iMQ8Dhs95nqB4AXOG7Taj7G4ra_medium.webp","\/storage\/images\/resized\/ex6KJoZujZOZFZh7jGfeHauiftuB3CI7iwJVFRDg_medium.webp","\/storage\/images\/resized\/MjH1ITP7lMYGxeqUZfkt2BnVLgjkk413jwBV97XX_medium.webp","\/storage\/images\/resized\/mxFdPe9qujsfvfYfcN0QOclAiYORFb0xrRlwV8gs_medium.webp","\/storage\/images\/resized\/9Mus3KG1Tkd7Bwaurt8H3RwWh0CxRlGoO6ng9UK1_medium.webp"],"datasets":[{"label":"","data":[60,37,14,11,4,2,1,1,1],"backgroundColor":["#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6"],"percentage":[45.11,27.82,10.53,8.27,3.01,1.5,0.75,0.75,0.75],"barThickness":13}]},"options":{"indexAxis":"y","maintainAspectRatio":false,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"},"stacked":false},"x":{"ticks":{"stepSize":null,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"},"stacked":false}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Publishers","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}},"yearsCitationsQuartiles":{"type":"bar","data":{"show":true,"labels":[2007,2008,2009,2010,2011,2012,2013,2014,2015,2016,2017,2018,2019,2020,2021,2022,2023,2024],"ids":[],"codes":[],"imageUrls":[],"datasets":[{"label":"Q4","backgroundColor":"rgb(221,90,78)","data":[0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0],"percentage":["0","0","0","0","0","0","0","0","0","0","0","0","0","0","0","0","0","0"]},{"label":"Q3","backgroundColor":"rgb(251, 163,83)","data":[0,0,0,0,0,0,1,1,1,0,0,1,0,0,1,0,0,0],"percentage":["0","0","0","0","0","0","0.75","0.75","0.75","0","0","0.75","0","0","0.75","0","0","0"]},{"label":"Q2","backgroundColor":"rgb(232, 213, 89)","data":[1,0,1,1,2,1,1,0,1,0,2,1,0,1,2,0,0,0],"percentage":["0.75","0","0.75","0.75","1.5","0.75","0.75","0","0.75","0","1.5","0.75","0","0.75","1.5","0","0","0"]},{"label":"Q1","backgroundColor":"rgb(164, 207, 99)","data":[7,8,10,5,9,7,5,7,3,7,3,4,4,8,5,1,1,2],"percentage":["5.26","6.02","7.52","3.76","6.77","5.26","3.76","5.26","2.26","5.26","2.26","3.01","3.01","6.02","3.76","0.75","0.75","1.5"]},{"label":"Quartile not defined","backgroundColor":"#E5E7EB","data":[0,3,1,0,0,1,2,5,2,2,1,0,0,0,1,0,0,0],"percentage":["0","2.26","0.75","0","0","0.75","1.5","3.76","1.5","1.5","0.75","0","0","0","0.75","0","0","0"]}]},"options":{"indexAxis":"x","maintainAspectRatio":true,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"},"stacked":true},"x":{"ticks":{"stepSize":1,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"},"stacked":true}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Citations quartiles by SCImago per year","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}},"yearsCitationsQuartilesWs":{"type":"bar","data":{"show":true,"labels":[2007,2008,2009,2010,2011,2012,2013,2014,2015,2016,2017,2018,2019,2020,2021,2022,2023,2024],"ids":[],"codes":[],"imageUrls":[],"datasets":[{"label":"Q4","backgroundColor":"rgb(221,90,78)","data":[0,0,0,0,0,0,0,0,1,0,0,0,0,0,1,0,0,0],"percentage":["0","0","0","0","0","0","0","0","0.75","0","0","0","0","0","0.75","0","0","0"]},{"label":"Q3","backgroundColor":"rgb(251, 163,83)","data":[0,0,0,0,0,1,0,1,1,0,0,0,0,1,0,0,0,0],"percentage":["0","0","0","0","0","0.75","0","0.75","0.75","0","0","0","0","0.75","0","0","0","0"]},{"label":"Q2","backgroundColor":"rgb(232, 213, 89)","data":[3,6,4,3,3,3,4,3,1,4,2,3,0,4,4,0,0,0],"percentage":["2.26","4.51","3.01","2.26","2.26","2.26","3.01","2.26","0.75","3.01","1.5","2.26","0","3.01","3.01","0","0","0"]},{"label":"Q1","backgroundColor":"rgb(164, 207, 99)","data":[4,2,6,3,7,3,3,4,2,3,3,3,4,4,3,1,1,2],"percentage":["3.01","1.5","4.51","2.26","5.26","2.26","2.26","3.01","1.5","2.26","2.26","2.26","3.01","3.01","2.26","0.75","0.75","1.5"]},{"label":"Quartile not defined","backgroundColor":"#E5E7EB","data":[1,3,2,0,1,2,2,5,2,2,1,0,0,0,1,0,0,0],"percentage":["0.75","2.26","1.5","0","0.75","1.5","1.5","3.76","1.5","1.5","0.75","0","0","0","0.75","0","0","0"]}]},"options":{"indexAxis":"x","maintainAspectRatio":true,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"},"stacked":true},"x":{"ticks":{"stepSize":1,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"},"stacked":true}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Citations quartiles by WoS per year","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}}}
Are you a researcher?
Create a profile to get free access to personal recommendations for colleagues and new articles.
Metrics
Cite this
GOST |
RIS |
BibTex |
MLA
Cite this
GOST
Copy
Romero P. E., Piers W. E. Mechanistic Studies on 14-Electron Ruthenacyclobutanes: Degenerate Exchange with Free Ethylene // Journal of the American Chemical Society. 2007. Vol. 129. No. 6. pp. 1698-1704.
GOST all authors (up to 50)
Copy
Romero P. E., Piers W. E. Mechanistic Studies on 14-Electron Ruthenacyclobutanes: Degenerate Exchange with Free Ethylene // Journal of the American Chemical Society. 2007. Vol. 129. No. 6. pp. 1698-1704.
Cite this
RIS
Copy
TY - JOUR
DO - 10.1021/ja0675245
UR - https://doi.org/10.1021/ja0675245
TI - Mechanistic Studies on 14-Electron Ruthenacyclobutanes: Degenerate Exchange with Free Ethylene
T2 - Journal of the American Chemical Society
AU - Romero, Patricio E
AU - Piers, Warren E.
PY - 2007
DA - 2007/01/23 00:00:00
PB - American Chemical Society (ACS)
SP - 1698-1704
IS - 6
VL - 129
SN - 0002-7863
SN - 1520-5126
ER -
Cite this
BibTex
Copy
@article{2007_Romero,
author = {Patricio E Romero and Warren E. Piers},
title = {Mechanistic Studies on 14-Electron Ruthenacyclobutanes: Degenerate Exchange with Free Ethylene},
journal = {Journal of the American Chemical Society},
year = {2007},
volume = {129},
publisher = {American Chemical Society (ACS)},
month = {jan},
url = {https://doi.org/10.1021/ja0675245},
number = {6},
pages = {1698--1704},
doi = {10.1021/ja0675245}
}
Cite this
MLA
Copy
Romero, Patricio E., and Warren E. Piers. “Mechanistic Studies on 14-Electron Ruthenacyclobutanes: Degenerate Exchange with Free Ethylene.” Journal of the American Chemical Society, vol. 129, no. 6, Jan. 2007, pp. 1698-1704. https://doi.org/10.1021/ja0675245.