Organic chemistry of subvalent transition metal complexes. 12. Hydrodesulfurization of organosulfur heterocycles by metal hydride-nickel(0) complexes: accelerated single-electron transfer in carbon-sulfur bond cleavage

1986 ◽  
Vol 108 (24) ◽  
pp. 7763-7767 ◽  
Author(s):  
john J. Eisch ◽  
Lawrence E. Hallenbeck ◽  
Kyoung Im. Han
Keyword(s):  
Organic Chemistry ◽  
Electron Transfer ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Metal Hydride ◽  
Bond Cleavage ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Sulfur Bond

Photoinduced transition-metal and external photosensitizer free cross-coupling of aryl triflates with trialkyl phosphites

2021 ◽  
Author(s):  
Qian Dou ◽  
Li Geng ◽  
Bin Cheng ◽  
Chao-Jun Li ◽  
Huiying Zeng
Keyword(s):  
Electron Transfer ◽  
Transition Metal ◽  
Bond Cleavage ◽  
Cross Coupling ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Rearrangement Process ◽  
Trialkyl Phosphites

Photoinduced phosphonation of aryl triflates with trialkyl phosphites via a tandem single-electron-transfer, C–O bond cleavage and Arbuzov rearrangement process in the absence of transition-metal and external photosensitizer is reported herein....

scholarly journals The Exchange of Cyclometalated Ligands

Molecules ◽  
2021 ◽  
Vol 26 (1) ◽  
pp. 210
Author(s):  
Alexander D. Ryabov
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Cyclopalladated Complexes ◽  
Derivatives Of ◽  
Cyclometalated Ligand ◽  
Incoming Ligand

Reactions of cyclometalated compounds are numerous. This account is focused on one of such reactions, the exchange of cyclometalated ligands, a reaction between a cyclometalated compound and an incoming ligand that replaces a previously cyclometalated ligand to form a new metalacycle: + H-C*~Z ⇄ + H-C~Y. Originally discovered for PdII complexes with Y/Z = N, P, S, the exchange appeared to be a mechanistically challenging, simple, and convenient routine for the synthesis of cyclopalladated complexes. Over four decades it was expanded to cyclometalated derivatives of platinum, ruthenium, manganese, rhodium, and iridium. The exchange, which is also questionably referred to as transcyclometalation, offers attractive synthetic possibilities and assists in disclosing key mechanistic pathways associated with the C–H bond activation by transition metal complexes and C–M bond cleavage. Both synthetic and mechanistic aspects of the exchange are reviewed and discussed.

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