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Year of publication
Has Fulltext
- yes (211) (remove)
Is part of the Bibliography
- no (211)
Keywords
- crystal structure (34)
- hydrogen bonding (11)
- X-Ray Structure Analysis (7)
- TATD (4)
- Schiff bases (3)
- benzoxazines (3)
- co-crystalline adducts (3)
- phenolic resins (3)
- silicon (3)
- NHC (2)
Institute
- Biochemie und Chemie (194)
- Biochemie, Chemie und Pharmazie (11)
- Medizin (6)
- Physik (2)
The intriguing (μ-hydrido)diboranes(4) with their prominent pristine representative [B2H5]− have mainly been studied theoretically. We now describe the behavior of the planarized tetraaryl (μ-hydrido)diborane(4) anion [1H]− in cycloaddition reactions with the homologous series of heterocumulenes CO2, iPrNCO, and iPrNCNiPr. We show that a C=O bond of CO2 selectively activates the B−B bond of [1H]−, while the μ-H ligand is left untouched ([2H]−). The carbodiimide iPrNCNiPr, in contrast, neglects the B−B bond and rather adds the B-bonded H− ion to its central C atom to generate a formamidinate bridge across the B2 pair ([3]−). As a hybrid, the isocyanate iPrNCO combines the reactivity patterns of both its congeners and gives two products: one of them ([4H]−) is related to [2H]−, the other ([5]−) is an analog of [3]−. 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.