scholarly journals Time resolved infrared studies of C-H bond activation by organometallics

1998 ◽  
Author(s):  
M.C. Asplund
Keyword(s):  
Bond Activation ◽  
Time Resolved ◽  
Infrared Studies

Time-resolved infrared studies of gas-phase coordinatively unsaturated photofragments (.eta.5-C5H5)Mn(CO)x (x = 2 and 1)

1992 ◽  
Vol 96 (19) ◽  
pp. 7650-7656 ◽  
Author(s):  
Youfeng Zheng ◽  
Wenhua Wang ◽  
Jingu Lin ◽  
Yongbo She ◽  
Kejian Fu
Keyword(s):  
Gas Phase ◽  
Time Resolved ◽  
Infrared Studies

Ultrafast Infrared Studies of Bond Activation in Organometallic Complexes

1999 ◽  
Vol 32 (7) ◽  
pp. 551-560 ◽  
Author(s):  
Haw Yang ◽  
Kenneth T. Kotz ◽  
Matthew C. Asplund ◽  
Matthew J. Wilkens ◽  
Charles B. Harris
Keyword(s):  
Bond Activation ◽  
Organometallic Complexes ◽  
Infrared Studies ◽  
Ultrafast Infrared

scholarly journals Femtosecond Infrared Studies of Chemical Bond Activation

1999 ◽  
Vol 19 (1-4) ◽  
pp. 253-262 ◽  
Author(s):  
M. C. Asplund ◽  
H. Yang ◽  
K. T. Kotz ◽  
S. E. Bromberg ◽  
M. J. Wilkens ◽  
...  
Keyword(s):  
Infrared Spectroscopy ◽  
Chemical Bond ◽  
Bond Activation ◽  
Product Formation ◽  
Organometallic Complexes ◽  
Activation Time ◽  
Activation Reaction ◽  
Infrared Studies ◽  
Important Intermediate ◽  
Solvent Complex

The identification of the intermediates observed in bond activation reactions involving organometallic complexes on time scales from femtoseconds to milliseconds has been accomplished through the use of ultrafast infrared spectroscopy. C—H bond activation by the molecule Tp*Rh(CO)2 showed a final activation time of 200 ns in cyclic solvents, indicating a reaction barrier of 8.3 kcal/mol. An important intermediate is the partially dechelated η2-Tp*Rh(CO)(S) solvent complex, which was formed 200 ps after the initial photoexcitation. Si—H bond activation by CpM(CO)3 (M=Mn, Re) showed some product formation in less than 5 ps, indicating that the Si—H activation reaction is barrierless. The activated product was formed on several timescales, from picoseconds to nanoseconds, suggesting that there are different pathways for forming final product which are partitioned by the initial photoexcitation.

Time-Resolved Infrared Studies of a Trimethylphosphine Model Derivative of [FeFe]-Hydrogenase

2013 ◽  
Vol 117 (49) ◽  
pp. 15792-15803 ◽  
Author(s):  
Melissa Johnson ◽  
James Thuman ◽  
Roger G. Letterman ◽  
Christopher J. Stromberg ◽  
Charles Edwin Webster ◽  
...  
Keyword(s):  
Time Resolved ◽  
Infrared Studies

Time-Resolved Infrared Studies on Two Isomeric Ruthenium(II)/Rhenium(I) Complexes Containing a Nonsymmetric Quaterpyridine Bridging Ligand

1998 ◽  
Vol 37 (10) ◽  
pp. 2598-2601 ◽  
Author(s):  
Jon R. Schoonover ◽  
Andrew P. Shreve ◽  
R. Brian Dyer ◽  
Rosemary L. Cleary ◽  
Michael D. Ward ◽  
...  
Keyword(s):  
Time Resolved ◽  
Bridging Ligand ◽  
Infrared Studies

scholarly journals Nanosecond Time-Resolved and Steady-State Infrared Studies of Photoinduced Decomposition of TATB at Ambient and Elevated Pressure

2009 ◽  
Vol 113 (20) ◽  
pp. 5881-5887 ◽  
Author(s):  
Elizabeth A. Glascoe ◽  
Joseph M. Zaug ◽  
Michael R. Armstrong ◽  
Jonathan C. Crowhurst ◽  
Christian D. Grant ◽  
...  
Keyword(s):  
Steady State ◽  
Elevated Pressure ◽  
Time Resolved ◽  
Infrared Studies

scholarly journals The Role of Structural Flexibility in Plasmon-Driven Coupling Reactions: Kinetic Limitations in the Dimerization of Nitro-Benzenes

2021 ◽  
Author(s):  
Wouter Koopman ◽  
Evgenii Titov ◽  
Radwan Mohamed Sarhan ◽  
Tina Gaebel ◽  
Robin Schürmann ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Photoelectron Spectroscopy ◽  
Density Functional ◽  
Bond Activation ◽  
Density Functional Theory Calculations ◽  
Surface Enhanced Raman Spectroscopy ◽  
Bimolecular Reaction ◽  
Structural Flexibility ◽  
Coupling Reactions ◽  
Time Resolved

<div>The plasmon-driven dimerization of 4-nitrothiophenol (4NTP) to 4-4’-dimercaptoazobenzene (DMAB) has become a testbed for understanding bimolecular photoreactions enhanced by nanoscale metals, in particular, regarding the relevance of electron transfer and heat transfer from the metal to the molecule. By adding a methylene group between the thiol bond and the nitrophenyl, we add structural flexibility to the reactant molecule. Time-resolved surface-enhanced Raman-spectroscopy proves that this (4-nitrobenzyl)mercaptan (4NBM) molecule has a larger dimerization rate and dimerization yield than 4NTP and higher selectivity towards dimerization. X-ray photoelectron spectroscopy and density functional theory calculations show that the electron transfer would prefer activation of 4NTP over 4NBM. We conclude that the rate limiting step of this plasmonic reaction is the dimerization step, which is dramatically enhanced by the additional flexibility of the reactant. This study may serve as an example for using nanoscale metals to simultaneously provide charge carriers for bond activation and localized heat for driving bimolecular reaction steps. The molecular structure of reactants can be tuned to control the reaction kinetics.<br></div>

Sign in / Sign up

Export Citation Format

Share Document