Precise Activation of Ammonia and Carbon Dioxide by an Iminodisilene

Wendel, Daniel; Szilvási, Tibor; Henschel, Daniel; Altmann, Philipp J.; Jandl, Christian; Inoue, Shigeyoshi; Rieger, Bernhard

doi:10.1002/anie.201804472

Cited by 60 publications

(38 citation statements)

References 34 publications

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“…The resulting planar 4‐membered Al−Al−C−O ring is structurally analogous to the related diboron and disilicon compounds . Retention of the carbonyl moiety exocyclic to the ring was confirmed by IR spectroscopy (1640 cm −1 ), which is in good agreement with the calculated value (1658 cm −1 ).…”

Section: Figuresupporting

confidence: 82%

CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

Weetman¹,

Bag²,

Szilvási

et al. 2019

Angew Chem Int Ed

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CO2 fixation and reduction to value‐added products is of utmost importance in the battle against rising CO2 levels in the Earth's atmosphere. An organoaluminum complex containing a formal aluminum double bond (dialumene), and thus an alkene equivalent, was used for the fixation and reduction of CO2. The CO2 fixation complex undergoes further reactivity in either the absence or presence of additional CO2, resulting in the first dialuminum carbonyl and carbonate complexes, respectively. Dialumene (1) can also be used in the catalytic reduction of CO2, providing selective formation of a formic acid equivalent via the dialuminum carbonate complex rather than a conventional aluminum–hydride‐based cycle. Not only are the CO2 reduction products of interest for C1 added value products, but the organoaluminum complexes isolated represent a significant step forward in the isolation of reactive intermediates proposed in many industrially relevant catalytic processes.

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Section: Figuresupporting

confidence: 82%

CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

Weetman¹,

Bag²,

Szilvási

et al. 2019

Angew Chem Int Ed

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“…[14,16] Retention of the carbonyl moiety exocyclic to the ring was confirmed by IR spectroscopy (1640 cm À1 ), which is in good agreement with the calculated value (1658 cm À1 ). [14,16] Retention of the carbonyl moiety exocyclic to the ring was confirmed by IR spectroscopy (1640 cm À1 ), which is in good agreement with the calculated value (1658 cm À1 ).…”

supporting

confidence: 87%

“…Ther esulting planar 4-membered AlÀAlÀCÀOr ing is structurally analogous to the related diboron and disilicon compounds. [14,16] Retention of the carbonyl moiety exocyclic to the ring was confirmed by IR spectroscopy (1640 cm À1 ), which is in good agreement with the calculated value (1658 cm À1 ). As expected, the AlÀAl distance in 2 is longer than that of 1 (2.585(2) vs.2 .3943(16) ,r espectively), indicating loss of double-bond character,a nd is now in the range of at ypical Al À Al single bond (2.53-2.75 ).…”

supporting

confidence: 86%

“…Frustrated Lewis pairs (FLPs) [9][10][11] and polar main-group multiple bonds have proven to be efficient methods for CO 2 activation. [15,16] Theresulting E À E À C À O(E= BorSi) 4-membered rings were found to be thermally unstable and undergo C À O cleavage-based reactivity. [15,16] Theresulting E À E À C À O(E= BorSi) 4-membered rings were found to be thermally unstable and undergo C À O cleavage-based reactivity.…”

mentioning

confidence: 99%

“…[12,13] In terms of non-polar multiply bonded main-group compounds,C O 2 activation has been shown to proceed by an initial [2+ +2]-cycloaddition for diborenes [14] and disilenes. [15,16] Theresulting E À E À C À O(E= BorSi) 4-membered rings were found to be thermally unstable and undergo C À O cleavage-based reactivity.…”

mentioning

confidence: 99%

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CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

Weetman¹,

Bag²,

Szilvási

et al. 2019

Angewandte Chemie

Self Cite

View full text Add to dashboard Cite

CO 2 fixation and reduction to value-added products is of utmost importance in the battle against rising CO 2 levels in the Earthsa tmosphere.A no rganoaluminum complex containing aformal aluminum double bond (dialumene), and thus an alkene equivalent, was used for the fixation and reduction of CO 2 .The CO 2 fixation complex undergoes further reactivity in either the absence or presence of additional CO 2 ,r esulting in the first dialuminum carbonyl and carbonate complexes, respectively.D ialumene (1)c an also be used in the catalytic reduction of CO 2 ,p roviding selective formation of af ormic acid equivalent via the dialuminum carbonate complex rather than aconventional aluminum-hydride-basedc ycle.N ot only are the CO 2 reduction products of interest for C 1 added value products,b ut the organoaluminum complexes isolated represent as ignificant step forwardi nt he isolation of reactive intermediates proposed in many industrially relevant catalytic processes.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Low Valent Main Group Compounds in Small Molecule Activation

Weetman

2021

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Since the discovery that main group elements can mimic transition metals, efforts have focussed on harnessing main group elements' abilities to break strong bonds to enable new sustainable methodologies. In this regard, use of small molecules, such as those found in greenhouse gases, is a prime target for incorporation into catalytic cycles to produce value‐added products. Initial challenges in main group chemistry focussed on the ability to isolate these highly reactive low‐oxidation state species, whilst also maintaining the reactive sites. An array of low valent compounds have been successfully isolated (i.e., multiple bonds, tetrylenes, anions, and cations), through careful ligand design, and have challenged traditional bonding models and preconceptions of the main group elements. Current advances have highlighted how reactive these low‐valent sites are with the ability to activate strong bonds, such as those found in small molecules (e.g., H 2 , CO, CO 2 , etc.). This represents the first step in a redox‐based catalytic cycle, as the low‐valent main group center undergoes oxidative addition reactions. Current challenges remain in reductive elimination, and thus functionalization of the small molecule, but examples of low‐valent main group elements in catalysis are starting to emerge and represent a bright future for main group chemistry. This article highlights the achievements of low valent main group elements, with a focus on group 2, 13, and 14 elements, in small molecule activation as well as the fundamental concepts that have aided the development of this rapidly advancing field.

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Precise Activation of Ammonia and Carbon Dioxide by an Iminodisilene

Cited by 60 publications

References 34 publications

CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

Low Valent Main Group Compounds in Small Molecule Activation

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Precise Activation of Ammonia and Carbon Dioxide by an Iminodisilene

Cited by 60 publications

References 34 publications

CO2Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

CO2Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

CO2Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

Low Valent Main Group Compounds in Small Molecule Activation

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CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond

CO₂Fixation and Catalytic Reduction by a Neutral Aluminum Double Bond