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

ChemInform Abstract: Ultrafast Infrared Studies of Bond Activation in Organometallic Complexes

ChemInform ◽  
2010 ◽  
Vol 30 (40) ◽  
pp. no-no
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.

Ultrafast Infrared Studies of the Reaction Mechanism of Silicon−Hydrogen Bond Activation by η5-CpV(CO)4

1999 ◽  
Vol 103 (49) ◽  
pp. 10426-10432 ◽  
Author(s):  
Preston T. Snee ◽  
Haw Yang ◽  
Kenneth T. Kotz ◽  
Christine K. Payne ◽  
Charles B. Harris
Keyword(s):  
Hydrogen Bond ◽  
Reaction Mechanism ◽  
Bond Activation ◽  
Infrared Studies ◽  
Ultrafast Infrared

ChemInform Abstract: Ultrafast Infrared Studies of the Role of Spin States in Organometallic Reaction Dynamics

ChemInform ◽  
2014 ◽  
Vol 45 (26) ◽  
pp. no-no
Author(s):  
Justin P. Lomont ◽  
Son C. Nguyen ◽  
Charles B. Harris
Keyword(s):  
Reaction Dynamics ◽  
Spin States ◽  
Infrared Studies ◽  
Ultrafast Infrared

scholarly journals Rhodium and Iridium Mediated C-H and O-H Bond Activation of Two Schiff Base Ligands: Synthesis, Characterization and Catalytic Properties of the Organometallic Complexes

2021 ◽  
Vol 9 ◽  
Author(s):  
Poulami Sengupta ◽  
Rituparna Das ◽  
Papu Dhibar ◽  
Piyali Paul ◽  
Samaresh Bhattacharya
Keyword(s):  
Schiff Base ◽  
Density Functional ◽  
Bond Activation ◽  
Density Functional Theory Method ◽  
Organometallic Complexes ◽  
Similar Reaction ◽  
Coupling Reactions ◽  
Schiff Base Ligands ◽  
Positive Side ◽  
Imine Ligands

Reaction of [Rh(PPh3)3Cl] with two Schiff base ligands, viz. N-(2′-hydroxyphenyl)furan-2-aldimine (H2L1) and N-(2′-hydroxyphenyl)thiophene-2-aldimine (H2L2), in refluxing toluene affords organorhodium complexes of type [Rh(PPh3)2(L)Cl] (L = L1 and L2). Similar reaction with [Ir(PPh3)3Cl] yields organoiridium complexes of type [Ir(PPh3)2(L) (H)] (L = L1 and L2). Crystal structures of [Rh(PPh3)2(L1)Cl] and [Ir(PPh3)2(L2) (H)] have been determined, where the imine ligands are found to bind to the metal centers as CNO-donors. Structures of [Rh(PPh3)2(L2)Cl] and [Ir(PPh3)2(L1) (H)] have been optimized by density functional theory method. Formation of the organometallic complexes is believed to proceed via C-H and O-H bond activation of the imine ligands. All four complexes show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry on the complexes shows an oxidation on the positive side of SCE and a reduction on the negative side. The organoiridium complexes are found to efficiently catalyze Suzuki-type C-C cross coupling reactions.

Sign in / Sign up

Export Citation Format

Share Document