{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"omics_type":["Unknown"],"volume":["60(24)"],"submitter":["Trageser T"],"funding":["Fonds der Chemischen Industrie"],"pubmed_abstract":["The intriguing (μ-hydrido)diboranes(4) with their prominent pristine representative [B<sub>2</sub> H<sub>5</sub> ]<sup>-</sup> have mainly been studied theoretically. We now describe the behavior of the planarized tetraaryl (μ-hydrido)diborane(4) anion [1H]<sup>-</sup> in cycloaddition reactions with the homologous series of heterocumulenes CO<sub>2</sub> , iPrNCO, and iPrNCNiPr. We show that a C=O bond of CO<sub>2</sub> selectively activates the B-B bond of [1H]<sup>-</sup> , while the μ-H ligand is left untouched ([2H]<sup>-</sup> ). The carbodiimide iPrNCNiPr, in contrast, neglects the B-B bond and rather adds the B-bonded H<sup>-</sup> ion to its central C atom to generate a formamidinate bridge across the B<sub>2</sub> pair ([3]<sup>-</sup> ). As a hybrid, the isocyanate iPrNCO combines the reactivity patterns of both its congeners and gives two products: one of them ([4H]<sup>-</sup> ) is related to [2H]<sup>-</sup> , the other ([5]<sup>-</sup> ) is an analog of [3]<sup>-</sup> . We finally propose a mechanistic scenario that rationalizes the individual reaction outcomes and combines them to a coherent picture of B-B vs. B-H bond activation."],"journal":["Angewandte Chemie (International ed. in English)"],"pagination":["13500-13506"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC8252796"],"repository":["biostudies-literature"],"pubmed_title":["B-B vs. B-H Bond Activation in a (μ-Hydrido)diborane(4) Anion upon Cycloaddition with CO<sub>2</sub> , Isocyanates, or Carbodiimides."],"pmcid":["PMC8252796"],"pubmed_authors":["Bolte M","Bebej D","Trageser T","Wagner M","Lerner HW"],"additional_accession":[]},"is_claimable":false,"name":"B-B vs. B-H Bond Activation in a (μ-Hydrido)diborane(4) Anion upon Cycloaddition with CO<sub>2</sub> , Isocyanates, or Carbodiimides.","description":"The intriguing (μ-hydrido)diboranes(4) with their prominent pristine representative [B<sub>2</sub> H<sub>5</sub> ]<sup>-</sup> have mainly been studied theoretically. We now describe the behavior of the planarized tetraaryl (μ-hydrido)diborane(4) anion [1H]<sup>-</sup> in cycloaddition reactions with the homologous series of heterocumulenes CO<sub>2</sub> , iPrNCO, and iPrNCNiPr. We show that a C=O bond of CO<sub>2</sub> selectively activates the B-B bond of [1H]<sup>-</sup> , while the μ-H ligand is left untouched ([2H]<sup>-</sup> ). The carbodiimide iPrNCNiPr, in contrast, neglects the B-B bond and rather adds the B-bonded H<sup>-</sup> ion to its central C atom to generate a formamidinate bridge across the B<sub>2</sub> pair ([3]<sup>-</sup> ). As a hybrid, the isocyanate iPrNCO combines the reactivity patterns of both its congeners and gives two products: one of them ([4H]<sup>-</sup> ) is related to [2H]<sup>-</sup> , the other ([5]<sup>-</sup> ) is an analog of [3]<sup>-</sup> . We finally propose a mechanistic scenario that rationalizes the individual reaction outcomes and combines them to a coherent picture of B-B vs. B-H bond activation.","dates":{"release":"2021-01-01T00:00:00Z","publication":"2021 Jun","modification":"2024-11-20T19:09:22.925Z","creation":"2022-02-10T19:47:14.094Z"},"accession":"S-EPMC8252796","cross_references":{"pubmed":["33740318"],"doi":["10.1002/anie.202103427"]}}