Hemilabile N-Xylyl-N′-methylperimidine Carbene Iridium Complexes as Catalysts for C–H Activation and Dehydrogenative Silylation: Dual Role of N-Xylyl Moiety for ortho-C–H Bond Activation and Reductive Bond Cleavage

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

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On the role of the surface oxygen species during A–H (A = C, N, O) bond activation: a density functional theory study

Chemical Communications ◽

10.1039/c4cc08658a ◽

2015 ◽

Vol 51 (13) ◽

pp. 2621-2624 ◽

Cited By ~ 28

Author(s):

Jong Suk Yoo ◽

Tuhin S. Khan ◽

Frank Abild-Pedersen ◽

Jens K. Nørskov ◽

Felix Studt

Keyword(s):

Density Functional ◽

Bond Activation ◽

Bond Cleavage ◽

Oxygen Species ◽

Final States ◽

Surface Oxygen ◽

Density Functional Theory Study ◽

Reaction Energy ◽

Functional Theory

During A–H (A = C, N, O) bond cleavage on O* or OH* pre-covered (111) surfaces, the oxygen species play the role of modifying the reaction energy by changing the species involved in the initial and final states of the reaction.

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Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

10.26434/chemrxiv.11742687.v1 ◽

2020 ◽

Author(s):

Shubham Deolka ◽

Orestes Rivada Wheelaghan ◽

Sandra Aristizábal ◽

Robert Fayzullin ◽

Shrinwantu Pal ◽

...

Keyword(s):

Alkyl Group ◽

Bond Activation ◽

Bond Cleavage ◽

Terminal Alkyne ◽

Alkyl Aryl ◽

Metal Metal ◽

The Stability ◽

Selective Formation ◽

Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

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Consecutive C–F bond activation and C–F bond formation of heteroaromatics at rhodium: the peculiar role of FSi(OEt)3

Chemical Science ◽

10.1039/c5sc00877h ◽

2015 ◽

Vol 6 (7) ◽

pp. 4255-4260 ◽

Cited By ~ 21

Author(s):

A. L. Raza ◽

T. Braun

Keyword(s):

Bond Activation ◽

Bond Cleavage ◽

Bond Formation ◽

Cleavage Reaction ◽

Bond Cleavage Reaction ◽

Consecutive Reactions ◽

Silyl Complex

C–F activation reactions for a silyl complex gave fluorosilane and Rh pyridyl complexes. In consecutive reactions, the fluorosilane can act as a fluoride source and a regeneration of the C–F bond occurs by Si–F bond cleavage. This sets back the C–F bond cleavage reaction with consequences for the overall chemoselectivity of the activation reactions.

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