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

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.

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

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.

Oxidative Addition of HSnR3 (R = Ph, Bu) to the Square-Planar Iridium(I) Compounds Ir(XR)(TFB)(PCy3) (XR = OMe, OEt, OCHMe2, OPh, SPr) and Ir(C2Ph)L2(PCy3) (L2 = TFB, 2CO)

1995 ◽  
Vol 14 (7) ◽  
pp. 3486-3496 ◽  
Author(s):  
Miguel A. Esteruelas ◽  
Fernando J. Lahoz ◽  
Montserrat Olivan ◽  
Enrique Onate ◽  
Luis A. Oro
Keyword(s):  
Oxidative Addition ◽  
Square Planar

scholarly journals [(1,2,5,6-η)-Cycloocta-1,5-diene](1-ethyl-3-isopropyl-1,3-imidazol-2-ylidene-κC2)(triphenylphosphane-κP)iridium(I) tetrafluoridoborate

IUCrData ◽  
2017 ◽  
Vol 2 (10) ◽  
Author(s):  
Karam B. Idrees ◽  
William J. Rutledge ◽  
Sue A. Roberts ◽  
Edward Rajaseelan
Keyword(s):  
Catalytic Activity ◽  
Title Compound ◽  
Complex Cation ◽  
Transfer Hydrogenation ◽  
Planar Geometry ◽  
Iridium Complex ◽  
Asymmetric Unit ◽  
Cationic Complex ◽  
Square Planar ◽  
Hydrogenation Reactions

In the title compound, [Ir(C8H12)(C8H14N2)(C18H15P)]BF4, the cationic complex has the anticipated square-planar geometry. The asymmetric unit comprises the iridium complex and one tetrafluoridoborate anion. The space group is non-centrosymmetric, with the Flack parameter of 0.007 (3) well determined, and confirms the hand for the complex cation. This compound shows promising catalytic activity in transfer hydrogenation reactions.

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