Divergent Reactivity of CO2 and CO and Related Substrates at the Nickel Carbon Double Bond of (PCcarbeneP)Ni(II) Pincer Complexes

2018 ◽  
Author(s):  
Etienne A. LaPierre ◽  
Warren Piers ◽  
Chris Gendy
Keyword(s):  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
Double Bond ◽  
Transfer Reactions ◽  
Pincer Complexes ◽  
Pincer Ligand ◽  
Group Transfer ◽  
Ligand Structure ◽  
Carbon Double Bond

The addition of carbon monoxide (CO), carbon dioxide (CO<sub>2</sub>) and isoelectronic isocyanide and isocyanates to the nickel carbene bond in PC<sub>carbene</sub>P pincer complexes is reported. For CO and CNR, irreversible group transfer reactions are observed, while for CO<sub>2</sub>, a reversible 2+2 addition to the carbene moiety occurs. The course of the CO and CO<sub>2</sub> reactions are strongly affected by the nature of the PC<sub>carbene</sub>P pincer ligand framework and a new more rigid ligand based on a 10,10-dimethyl-9,10-dihydroanthracene core was designed in order to study these reactions, illustrating the profound effect of small changes in ligand structure on reaction outcomes.

Divergent Reactivity of CO2 and CO and Related Substrates at the Nickel Carbon Double Bond of (PCcarbeneP)Ni(II) Pincer Complexes

2018 ◽  
Author(s):  
Etienne A. LaPierre ◽  
Warren Piers ◽  
Chris Gendy
Keyword(s):  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
Double Bond ◽  
Transfer Reactions ◽  
Pincer Complexes ◽  
Pincer Ligand ◽  
Group Transfer ◽  
Ligand Structure ◽  
Carbon Double Bond

The addition of carbon monoxide (CO), carbon dioxide (CO<sub>2</sub>) and isoelectronic isocyanide and isocyanates to the nickel carbene bond in PC<sub>carbene</sub>P pincer complexes is reported. For CO and CNR, irreversible group transfer reactions are observed, while for CO<sub>2</sub>, a reversible 2+2 addition to the carbene moiety occurs. The course of the CO and CO<sub>2</sub> reactions are strongly affected by the nature of the PC<sub>carbene</sub>P pincer ligand framework and a new more rigid ligand based on a 10,10-dimethyl-9,10-dihydroanthracene core was designed in order to study these reactions, illustrating the profound effect of small changes in ligand structure on reaction outcomes.

Tuning Iridium(I) PCcarbeneP Frameworks for Facile Cooperative N2O Reduction

2018 ◽  
Author(s):  
Joel D. Smith ◽  
Edwina Chih ◽  
Warren Piers ◽  
Denis M. Spasyuk
Keyword(s):  
Double Bond ◽  
Oxygen Atom ◽  
Kinetic Study ◽  
Atom Transfer ◽  
Oxygen Atom Transfer ◽  
N2o Reduction ◽  
Pincer Ligand ◽  
Selective Reaction ◽  
Carbon Double Bond

A semiquantitative kinetic study correlates the rate of oxygen atom transfer from N<sub>2</sub>O to an iridium carbon double bond with the donor properties of six PC<sub>carbene</sub>P pincer ligand frameworks. Two new rigid, electron rich ligands are described and shown to be the most effective for rapid, selective reaction with N<sub>2</sub>O.<br>

scholarly journals Activation of Si–H bonds across the nickel carbene bond in electron rich nickel PCcarbeneP pincer complexes

2016 ◽  
Vol 52 (7) ◽  
pp. 1361-1364 ◽  
Author(s):  
Etienne A. LaPierre ◽  
Warren E. Piers ◽  
Denis M. Spasyuk ◽  
David W. Bi
Keyword(s):  
Double Bond ◽  
Hydrogen Bonds ◽  
Pincer Complexes ◽  
Carbon Double Bond

Silicon–hydrogen bonds are shown to add to a nickel carbon double bond to yield nickel α-silylalkyl hydrido complexes.

The oxidation of iso butene catalyzed by hydrogen bromide

1962 ◽  
Vol 268 (1334) ◽  
pp. 405-423 ◽  
Keyword(s):  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
Double Bond ◽  
Small Proportion ◽  
Main Chain ◽  
Hydrogen Bromide ◽  
Inert Gas ◽  
Static System ◽  
Peroxy Radicals ◽  
Methyl Group

The oxidation of iso butene catalyzed by hydrogen bromide in a static system between 100 and 200 °C has been investigated. In a boric oxide coated vessel below about 170 °C the pressure decreased continually during the reaction, the rate accelerating rapidly to a maximum and then falling gradually and the main products being BrCH 2 .C(CH 3 ) 2 .OOH and a diperoxide. The reaction ceased after only a small proportion of the olefin was oxidized owing to the HBr being used up. At 145 °C ρ max. ∝ [C 4 H 8 ] 0.35 [O 2 ] 0.5 [HBr] 1.76 . Added inert gas or packing the vessel had little effect on the rate, but the reaction was accelerated by added bromine, t .-butyl hydroperoxide and di- t .-butylperoxide and retarded by added alcohols. At 195 °C the pressure decreased to a minimum and then rose, most of the iso butene being now oxidized and other products, CH 2 =C(CH 3 )CH 2 OOH, methacrolein, acetone, carbon monoxide, carbon dioxide and water being formed in appreciable yields. It is suggested that autocatalysis is due to the reaction of a small proportion of the hydroperoxides produced with HBr to give radicals, and that the main chain carriers are bromine atoms and peroxy radicals, the former either adding to the double bond of the olefin or at the higher temperatures abstracting hydrogen from a methyl group and the latter abstracting hydrogen from HBr to give the hydroperoxides, adding to the double bond of iso butene to give eventually diperoxides or at the higher temperatures decomposing.

Carbon monoxide insertion into a uranium carbon double bond. The structure of (.eta.5-C5H5)3U(.eta.2-OCCH)P(CH3)(C6H5)2

1982 ◽  
Vol 1 (6) ◽  
pp. 869-871 ◽  
Author(s):  
Roger E. Cramer ◽  
Richard B. Maynard ◽  
Josephine C. Paw ◽  
John W. Gilje
Keyword(s):  
Carbon Monoxide ◽  
Double Bond ◽  
Carbon Double Bond

Tuning Iridium(I) PCcarbeneP Frameworks for Facile Cooperative N2O Reduction

2018 ◽  
Author(s):  
Joel D. Smith ◽  
Edwina Chih ◽  
Warren Piers ◽  
Denis M. Spasyuk
Keyword(s):  
Double Bond ◽  
Oxygen Atom ◽  
Kinetic Study ◽  
Atom Transfer ◽  
Oxygen Atom Transfer ◽  
N2o Reduction ◽  
Pincer Ligand ◽  
Selective Reaction ◽  
Carbon Double Bond

A semiquantitative kinetic study correlates the rate of oxygen atom transfer from N<sub>2</sub>O to an iridium carbon double bond with the donor properties of six PC<sub>carbene</sub>P pincer ligand frameworks. Two new rigid, electron rich ligands are described and shown to be the most effective for rapid, selective reaction with N<sub>2</sub>O.<br>

Tuning Iridium(I) PCcarbeneP Frameworks for Facile Cooperative N2O Reduction

2018 ◽  
Author(s):  
Joel D. Smith ◽  
Edwina Chih ◽  
Warren Piers ◽  
Denis M. Spasyuk
Keyword(s):  
Double Bond ◽  
Oxygen Atom ◽  
Kinetic Study ◽  
Atom Transfer ◽  
Oxygen Atom Transfer ◽  
N2o Reduction ◽  
Pincer Ligand ◽  
Selective Reaction ◽  
Carbon Double Bond

A semiquantitative kinetic study correlates the rate of oxygen atom transfer from N<sub>2</sub>O to an iridium carbon double bond with the donor properties of six PC<sub>carbene</sub>P pincer ligand frameworks. Two new rigid, electron rich ligands are described and shown to be the most effective for rapid, selective reaction with N<sub>2</sub>O.<br>

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