Issue 40, 2023

A hampered oxidative addition of pre-coordinated pincer ligands can favour alternative pathways of activation

Abstract

Pre-coordination to a transition metal by the terminal donor groups of a tri-dentate ligand is a common strategy to stabilise elusive groups, to achieve unprecedented bond activation and to develop novel modes of metal–ligand-cooperation for catalysis. In the current manuscript, we demonstrate that the oxidative addition of a central E–H-bond after pre-coordination to the metal centre is disfavoured for metals with d10 electron configuration. For exemplary pincer ligands and metals with d10 electron configuration, quantum chemical calculations suggest a second barrier, which is associated with the rearrangement of the saw-horse structure, obtained after oxidative addition, to the expected square planar geometry for the resulting d8 electron configuration. In the case of PBP-type ligands with a central L2BH2-group (L = R3P) the reaction with Pt0 precursors proceeds via an alternative pathway of activation, which involves the backside attack of a nucleophile to the boron atom, which facilitates the nucleophilic attack of the Pt0 centre and formation of a boryl complex (LBH2). As the corresponding reaction with a PtII precursor leads to B–H- instead of B–L-activation and formation of complex 2 with a L2BH donor, our results show that ligand-stabilized borylenes (L2BH) can in principle be converted to boryls (LBH2) via boronium salts (L2BH2+).

Graphical abstract: A hampered oxidative addition of pre-coordinated pincer ligands can favour alternative pathways of activation

Supplementary files

Article information

Article type
Communication
Submitted
23 Cʼhwe. 2023
Accepted
12 Ebr. 2023
First published
14 Ebr. 2023

Chem. Commun., 2023,59, 6004-6007

A hampered oxidative addition of pre-coordinated pincer ligands can favour alternative pathways of activation

F. Wehmeyer and R. Langer, Chem. Commun., 2023, 59, 6004 DOI: 10.1039/D3CC00874F

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