Cobalt Boryl Complexes: Enabling and Exploiting Migratory Insertion in Base‐Metal‐Mediated Borylation1. Issue 33 (26th June 2015)

• Record Type: Journal Article
• Authors: Frank, René; Howell, James; Campos, Jésus; Tirfoin, Rémi; Phillips, Nicholas; Zahn, Stefan; Mingos, D. Michael P.; Aldridge, Simon
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 33(2015)
• Page Start: 9586
• Page End: 9590
• Publication Date: 2015-06-26
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201504929
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Cobalt boryl complexes, which have only been sporadically reported, can be accessed systematically with remarkable (but controllable) variation in the nature of the MB bond. Complexes incorporating a very strong <italic>trans</italic> σ‐donor display unparalleled inertness, reflected in retention of the MB bond even in the presence of extremely strong acid. By contrast, the use of the strong π‐acceptor CO in the <italic>trans</italic> position, results in significant CoB elongation and to labilization of the boryl ligand via unprecedented CO migratory insertion. Such chemistry provides a pathway for the generation of coordinative unsaturation, thereby enabling ligand substitution and/or substrate assimilation. Alkene functionalization by boryl transfer, a well‐known reaction for noble metals such as Rh or Pt, can thus be effected by an 18‐electron base‐metal complex.</p> </abstract>