0000000001038589
AUTHOR
Katherine N. Robertson
Mono‐ and Bis(imidazolidinium ethynyl) Cations and Reduction of the Latter To Give an Extended Bis‐1,4‐([3]Cumulene)‐p-carboquinoid System
An extended π-system containing two [3]cumulene fragments separated by a p-carboquinoid and stabilized by two capping N-heterocyclic carbenes (NHCs) has been prepared. Mono- and bis(imidazolidinium ethynyl) cations have also been synthesized from the reaction of an NHC with phenylethynyl bromide or 1,4-bis(bromoethynyl)benzene. Cyclic voltammetry coupled with synthetic and structural studies showed that the dication is readily reduced to a neutral, singlet bis-1,4-([3]cumulene)-p-carboquinoid as a result of the π-accepting properties of the capping NHCs. peerReviewed
A Simple Complex on the Verge of Breakdown: Isolation of the Elusive Cyanoformate Ion
Cyanide Hitches a Ride Cyanide is a by-product of the biosynthesis of ethylene in plants and it has been somewhat puzzling how the ion is safely removed before it can shut down enzymatic pathways by coordination to catalytic iron centers. A proposed mechanism has implicated the cyanoformate ion—essentially, a weak adduct of cyanide and carbon dioxide—as the initial product, although its lifetime was uncertain. Murphy et al. (p. 75 ; see the Perspective by Alabugin and Mohamed ) crystallized this previously elusive adduct and found that its solution-phase stability varies inversely with the dielectric properties of the medium. The results bolster a picture in which the adduct shuttles the cy…
Mono‐ and Bis(imidazolidinium ethynyl) Cations and Reduction of the Latter To Give an Extended Bis‐1,4‐([3]Cumulene)‐ p ‐carboquinoid System
An extended π-system containing two [3]cumulene fragments separated by a p-carboquinoid and stabilized by two capping N-heterocyclic carbenes (NHCs) has been prepared. Mono- and bis(imidazolidinium ethynyl) cations have also been synthesized from the reaction of an NHC with phenylethynyl bromide or 1,4-bis(bromoethynyl)benzene. Cyclic voltammetry coupled with synthetic and structural studies showed that the dication is readily reduced to a neutral, singlet bis-1,4-([3]cumulene)-p-carboquinoid as a result of the π-accepting properties of the capping NHCs.
Structurally simple complexes of CO2
The ability to bind CO2 through the formation of low-energy, easily-broken, bonds could prove invaluable in a variety of chemical contexts. For example, weak bonds to CO2 would greatly decrease the cost of the energy-intensive sorbent-regeneration step common to most carbon capture technologies. Furthermore, exploration of this field could lead to the discovery of novel CO2 chemistry. Reduction of complexed carbon dioxide might generate chemical feedstocks for the preparation of value-added products, particularly transportation fuels or fuel precursors. Implementation on a large scale could help to drastically reduce CO2 concentrations in the atmosphere. However, literature examples of weak…
Comment on "Crystallographic Snapshot of an Arrested Intermediate in the Biomimetic Activation of CO2"
Out of focus: A recent Communication published in this journal describes the synthesis of [nBu4N]HCO3. The authors performed a single-crystal X-ray study that revealed a putative species described as an incipient hydroxide ion engaging in a long, and presumably weak, interaction with CO2. Our recent exploration of the coordination chemistry of CO2 with small ions leads us to believe that such an exceptional bonding situation is unlikely. Instead, we argue that the crystal structure is that of [nBu4N]O2CCH3 and therefore not representative of the bulk powder from the synthesis. peerReviewed
Structurally simple complexes of CO2
The ability to bind CO2 through the formation of low-energy, easily-broken, bonds could prove invaluable in a variety of chemical contexts. For example, weak bonds to CO2 would greatly decrease the cost of the energy-intensive sorbent-regeneration step common to most carbon capture technologies. Furthermore, exploration of this field could lead to the discovery of novel CO2 chemistry. Reduction of complexed carbon dioxide might generate chemical feedstocks for the preparation of value-added products, particularly transportation fuels or fuel precursors. Implementation on a large scale could help to drastically reduce CO2 concentrations in the atmosphere. However, literature examples of weak…
Comment on “Crystallographic Snapshot of an Arrested Intermediate in the Biomimetic Activation of CO2”
Out of focus: A recent Communication published in this journal describes the synthesis of [nBu4 N]HCO3 . The authors performed a single-crystal X-ray study that revealed a putative species described as an incipient hydroxide ion engaging in a long, and presumably weak, interaction with CO2 . Our recent exploration of the coordination chemistry of CO2 with small ions leads us to believe that such an exceptional bonding situation is unlikely. Instead, we argue that the crystal structure is that of [nBu4 N]O2 CCH3 and therefore not representative of the bulk powder from the synthesis.
CCDC 1549500: Experimental Crystal Structure Determination
Related Article: Brian M. Barry, R. Graeme Soper, Juha Hurmalainen, Akseli Mansikkamäki, Katherine N. Robertson, William L. McClennan, Alex J. Veinot, Tracey L. Roemmele, Ulrike Werner-Zwanziger, René T. Boeré, Heikki M. Tuononen, Jason A. C. Clyburne, Jason D. Masuda|2018|Angew.Chem.,Int.Ed.|57|749|doi:10.1002/anie.201711031
CCDC 986380: Experimental Crystal Structure Determination
Related Article: Luke J. Murphy, Katherine N. Robertson, Scott G. Harroun, Christa L. Brosseau, Ulrike Werner-Zwanziger, Jani Moilanen, Heikki M. Tuononen, Jason A.C. Clyburne|2014|Science|344|75|doi:10.1126/science.1250808
CCDC 1549501: Experimental Crystal Structure Determination
Related Article: Brian M. Barry, R. Graeme Soper, Juha Hurmalainen, Akseli Mansikkamäki, Katherine N. Robertson, William L. McClennan, Alex J. Veinot, Tracey L. Roemmele, Ulrike Werner-Zwanziger, René T. Boeré, Heikki M. Tuononen, Jason A. C. Clyburne, Jason D. Masuda|2018|Angew.Chem.,Int.Ed.|57|749|doi:10.1002/anie.201711031
CCDC 1549502: Experimental Crystal Structure Determination
Related Article: Brian M. Barry, R. Graeme Soper, Juha Hurmalainen, Akseli Mansikkamäki, Katherine N. Robertson, William L. McClennan, Alex J. Veinot, Tracey L. Roemmele, Ulrike Werner-Zwanziger, René T. Boeré, Heikki M. Tuononen, Jason A. C. Clyburne, Jason D. Masuda|2018|Angew.Chem.,Int.Ed.|57|749|doi:10.1002/anie.201711031
CCDC 1549499: Experimental Crystal Structure Determination
Related Article: Brian M. Barry, R. Graeme Soper, Juha Hurmalainen, Akseli Mansikkamäki, Katherine N. Robertson, William L. McClennan, Alex J. Veinot, Tracey L. Roemmele, Ulrike Werner-Zwanziger, René T. Boeré, Heikki M. Tuononen, Jason A. C. Clyburne, Jason D. Masuda|2018|Angew.Chem.,Int.Ed.|57|749|doi:10.1002/anie.201711031
CCDC 1549503: Experimental Crystal Structure Determination
Related Article: Brian M. Barry, R. Graeme Soper, Juha Hurmalainen, Akseli Mansikkamäki, Katherine N. Robertson, William L. McClennan, Alex J. Veinot, Tracey L. Roemmele, Ulrike Werner-Zwanziger, René T. Boeré, Heikki M. Tuononen, Jason A. C. Clyburne, Jason D. Masuda|2018|Angew.Chem.,Int.Ed.|57|749|doi:10.1002/anie.201711031
CCDC 1036823: Experimental Crystal Structure Determination
Related Article: Juha Hurmalainen, Michael A. Land, Katherine N. Robertson, Christopher J. Roberts, Ian S. Morgan, Heikki M. Tuononen and Jason A. C. Clyburne|2015|Angew.Chem.,Int.Ed.|54|7484|doi:10.1002/anie.201411654
CCDC 1549498: Experimental Crystal Structure Determination
Related Article: Brian M. Barry, R. Graeme Soper, Juha Hurmalainen, Akseli Mansikkamäki, Katherine N. Robertson, William L. McClennan, Alex J. Veinot, Tracey L. Roemmele, Ulrike Werner-Zwanziger, René T. Boeré, Heikki M. Tuononen, Jason A. C. Clyburne, Jason D. Masuda|2018|Angew.Chem.,Int.Ed.|57|749|doi:10.1002/anie.201711031
CCDC 1549504: Experimental Crystal Structure Determination
Related Article: Brian M. Barry, R. Graeme Soper, Juha Hurmalainen, Akseli Mansikkamäki, Katherine N. Robertson, William L. McClennan, Alex J. Veinot, Tracey L. Roemmele, Ulrike Werner-Zwanziger, René T. Boeré, Heikki M. Tuononen, Jason A. C. Clyburne, Jason D. Masuda|2018|Angew.Chem.,Int.Ed.|57|749|doi:10.1002/anie.201711031