Redox-state dependent activation of silanes and ammonia with reverse polarity (PCcarbeneP)Ni complexes: electrophilic vs. nucleophilic carbenes

2018 ◽  
Vol 47 (46) ◽  
pp. 16789-16797 ◽  
Author(s):  
Etienne A. LaPierre ◽  
Warren E. Piers ◽  
Chris Gendy
Keyword(s):  
Redox State ◽  
Nickel Complexes ◽  
Synthesis And Characterization ◽  
Reverse Polarity ◽  
Nucleophilic Carbenes ◽  
State Dependent

A rigidified PCalkylP ligand allowed for the synthesis and characterization of cationic and radical PCCarbeneP nickel complexes in which the carbene anchor of the pincer framework is electrophilic rather than nucleophilic.

scholarly journals Redox–state Dependent Activation of Silanes and Ammonia with Reverse Polarity (PCcarbeneP)Ni Complexes: Electrophilic vs. Nucleophilic Carbenes

2018 ◽  
Author(s):  
Warren Piers ◽  
Etienne A. LaPierre ◽  
Chris Gendy
Keyword(s):  
Small Molecules ◽  
Redox State ◽  
Reverse Polarity ◽  
Carbene Complexes ◽  
Carbene Complex ◽  
Nucleophilic Carbenes ◽  
Bond Forming ◽  
State Dependent ◽  
Hydride Abstraction ◽  
Electron Reduction

A rigidified PC<sub>alkyl</sub>P ligand allowed for the synthesis and charactarization of cationic and radical PC<sub>Carbene</sub>P nickel complexes in which the carbene anchor of the pincer framework is electrophilic rather than nucleophilic. Alpha-hydride abstraction from (PC<sub>alkyl</sub>P)nickel halide complex readily leads to the cationic carbene complex, which furnishes the radical carbene complex by one electron reduction. The reactivity of these reverse polarity carbene complexes towards small molecules (H<sub>2</sub>, CO, CO<sub>2</sub>, R<sub>3</sub>SiH, NH<sub>3</sub>) reveals different modes of activation when compared to previously reported nucleophilic nickel carbene complexes, and a clear dependence on the redox state of the complex. For H<sub>2</sub>, CO and CO<sub>2</sub>, no reaction is observed, but silanes react via hydride transfer and formation of solvated silylium ions. Ammonia is activated in a novel way, wherein it coordinates the carbene carbon and is deprotonated to form a robust C-N bond. This is not only a rare example of ammonia activation by a first row transition metal but also evidence of the intermediacy of group 10 carbenes in direct C-N bond forming reactions.

scholarly journals Redox–state Dependent Activation of Silanes and Ammonia with Reverse Polarity (PCcarbeneP)Ni Complexes: Electrophilic vs. Nucleophilic Carbenes

2018 ◽  
Author(s):  
Warren Piers ◽  
Etienne A. LaPierre ◽  
Chris Gendy
Keyword(s):  
Small Molecules ◽  
Redox State ◽  
Reverse Polarity ◽  
Carbene Complexes ◽  
Carbene Complex ◽  
Nucleophilic Carbenes ◽  
Bond Forming ◽  
State Dependent ◽  
Hydride Abstraction ◽  
Electron Reduction

A rigidified PC<sub>alkyl</sub>P ligand allowed for the synthesis and charactarization of cationic and radical PC<sub>Carbene</sub>P nickel complexes in which the carbene anchor of the pincer framework is electrophilic rather than nucleophilic. Alpha-hydride abstraction from (PC<sub>alkyl</sub>P)nickel halide complex readily leads to the cationic carbene complex, which furnishes the radical carbene complex by one electron reduction. The reactivity of these reverse polarity carbene complexes towards small molecules (H<sub>2</sub>, CO, CO<sub>2</sub>, R<sub>3</sub>SiH, NH<sub>3</sub>) reveals different modes of activation when compared to previously reported nucleophilic nickel carbene complexes, and a clear dependence on the redox state of the complex. For H<sub>2</sub>, CO and CO<sub>2</sub>, no reaction is observed, but silanes react via hydride transfer and formation of solvated silylium ions. Ammonia is activated in a novel way, wherein it coordinates the carbene carbon and is deprotonated to form a robust C-N bond. This is not only a rare example of ammonia activation by a first row transition metal but also evidence of the intermediacy of group 10 carbenes in direct C-N bond forming reactions.

Progress in preparation and characterization of silylene iron, cobalt and nickel complexes

2021 ◽  
Author(s):  
Wenjing Yang ◽  
Yanhong Dong ◽  
Hongjian Sun ◽  
Xiaoyan Li
Keyword(s):  
Nickel Complexes ◽  
Electron Cloud ◽  
Synthesis And Characterization ◽  
Iron Cobalt ◽  
Cloud Density ◽  
Cobalt And Nickel

The synthesis and characterization of Fe, Co and Ni complexes supported by silylene ligands in recent ten years are summarized. Due to the decrease of electron cloud density on Si...

Synthesis and Characterization of [(NHC)Ni(styrene)2] Complexes: Isolation of Monocarbene Nickel Complexes and Benchmarking of %VBur in (NHC)Ni-π Systems

2018 ◽  
Vol 37 (21) ◽  
pp. 3687-3697 ◽  
Author(s):  
Stephanie Felten ◽  
Sarah F. Marshall ◽  
Alisa J. Groom ◽  
Ryan T. Vanderlinden ◽  
Ryan M. Stolley ◽  
...  
Keyword(s):  
Nickel Complexes ◽  
Synthesis And Characterization

Synthesis and Characterization of Linear and Square-Planar Nickel Complexes with Primary Amido Ligands

2008 ◽  
Vol 47 (9) ◽  
pp. 3468-3470 ◽  
Author(s):  
Jianfeng Li ◽  
Haibin Song ◽  
Chunming Cui ◽  
Jin-Pei Cheng
Keyword(s):  
Nickel Complexes ◽  
Synthesis And Characterization ◽  
Amido Ligands ◽  
Square Planar
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