Ambireactive (R3P)2BH2 Groups Facilitating Temperature‐Switchable Bond Activation by an Iron Complex. Issue 6 (15th December 2017)

• Record Type: Journal Article
• Authors: Vondung, Lisa; Sattler, Lars E.; Langer, Robert
• Is Part Of: Chemistry. Volume 24:Issue 6(2018)
• Page Start: 1358
• Page End: 1364
• Publication Date: 2017-12-15
• Subjects: boron -- C−H activation -- cooperative effects -- hydrides -- iron; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201704018
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: An iron pincer complex containing a hemi‐labile (R3 P)2 BH2 group exhibits temperature‐switchable reactivity patterns: a reversible B−H activation concomitant with a P−B bond cleavage is observed at room temperature. Below 4 °C, intra‐ and intermolecular C−H activation pathways are becoming faster and more dominant. Mechanistic investigations reveal that the lability of the (R3 P)2 BH2 group in combination with the exothermic formation of σ‐bonded complexes are responsible for the switchable bond activation. Finally, a protocol for an iron‐catalyzed H/D‐exchange of organic solvents in the absence of oxidants has been developed. Abstract : Flip the switch : Bond activation in an iron complex is switching at 4 °C from an intramolecular B−H to a C−H activation. The exothermic formation of σ‐complexes is likely to be responsible for the changing reactivity and it facilitates a catalytic H/D‐exchange of C−H‐bonds.