Cleavage of Ether, Ester, and Tosylate C(sp3)–O Bonds by an Iridium Complex, Initiated by Oxidative Addition of C–H Bonds. Experimental and Computational Studies

2013 ◽  
Vol 135 (13) ◽  
pp. 5127-5143 ◽  
Author(s):  
Sabuj Kundu ◽  
Jongwook Choi ◽  
David Y. Wang ◽  
Yuriy Choliy ◽  
Thomas J. Emge ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Iridium Complex ◽  
Computational Studies ◽  
Ether Ester

Evidence for a possible trans oxidative addition of hydrogen to an iridium complex

1979 ◽  
Vol 101 (14) ◽  
pp. 3987-3989 ◽  
Author(s):  
John F. Harrod ◽  
Gordon Hamer ◽  
William Yorke
Keyword(s):  
Oxidative Addition ◽  
Iridium Complex

Acid-Catalyzed Oxidative Addition of a C–H Bond to a Square Planar d8 Iridium Complex

2014 ◽  
Vol 136 (25) ◽  
pp. 8891-8894 ◽  
Author(s):  
Jason D. Hackenberg ◽  
Sabuj Kundu ◽  
Thomas J. Emge ◽  
Karsten Krogh-Jespersen ◽  
Alan S. Goldman
Keyword(s):  
Oxidative Addition ◽  
Iridium Complex ◽  
Square Planar ◽  
Acid Catalyzed

scholarly journals Oxidative addition of silicon hydrides to hydridocarbonyltris(triphenylphosphine)iridium(I)

1969 ◽  
Vol 47 (12) ◽  
pp. 2205-2208 ◽  
Author(s):  
J. F. Harrod ◽  
D. F. R. Gilson ◽  
R. Charles
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Oxidative Addition ◽  
Proton Nuclear Magnetic Resonance ◽  
Iridium Complex ◽  
Thermal Loss ◽  
Silicon Hydride ◽  
Silicon Hydrides ◽  
Nuclear Magnetic

Complexes have been prepared by oxidation of hydridocarbonyltris(triphenylphosphine)iridium(I) with a variety of silicon hydrides. The complexes were very stable with respect to thermal loss of either silicon hydride or molecular hydrogen.An unequivocal assignment of stereochemistry of the complexes was obtained from a combination of infrared and proton nuclear magnetic resonance (n.m.r.) techniques. Addition of the silicon hydride to the iridium complex was found to be stereospecifically cis.

scholarly journals Anti-selective [3+2] (Hetero)annulation of non-conjugated alkenes via directed nucleopalladation

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Hui-Qi Ni ◽  
Ilia Kevlishvili ◽  
Pranali G. Bedekar ◽  
Joyann S. Barber ◽  
Shouliang Yang ◽  
...  
Keyword(s):  
Natural Products ◽  
Functional Groups ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Direct Access ◽  
Computational Studies ◽  
Preliminary Results ◽  
Carbon Based

Abstract2,3-Dihydrobenzofurans and indolines are common substructures in medicines and natural products. Herein, we describe a method that enables direct access to these core structures from non-conjugated alkenyl amides and ortho-iodoanilines/phenols. Under palladium(II) catalysis this [3 + 2] heteroannulation proceeds in an anti-selective fashion and tolerates a wide variety of functional groups. N-Acetyl, -tosyl, and -alkyl substituted ortho-iodoanilines, as well as free –NH2 variants, are all effective. Preliminary results with carbon-based coupling partners also demonstrate the viability of forming indane core structures using this approach. Experimental and computational studies on reactions with phenols support a mechanism involving turnover-limiting, endergonic directed oxypalladation, followed by intramolecular oxidative addition and reductive elimination.

Activation entropy as a dominant factor in the oxidative addition of some group IV hydrides to an iridium(I) complex

1976 ◽  
Vol 54 (19) ◽  
pp. 3102-3109 ◽  
Author(s):  
J. P. Fawcett ◽  
J. F. Harrod
Keyword(s):  
Relative Rate ◽  
Oxidative Addition ◽  
Group Iv ◽  
Dominant Factor ◽  
Iridium Complex ◽  
Activation Entropy ◽  
Acid Base ◽  
Square Planar ◽  
The Difference ◽  
Kinetics Of

The kinetics of the reactions[Formula: see text]have been studied (M = Si, Ge, Sn). All three reactions proceed by predissociation of the iridium complex and concerted cis addition of Ph3MH to the square-planar intermediate. The relative rate of addition of Ph3MH increases in the order Si (1) < Ge (18) < Sn (70) and the difference in rate within experimental error is due entirely to change in ΔS0. It is concluded that, for this particular series of oxidative addition reactions, solvation effects related to a change in polarity on passage to the transition state are more important than bond energies, or acid–base properties, in determining relative reaction energetics. The relevance of entropy barriers to the problem of paraffin activation is discussed.

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