Unexpected Vulnerability of DPEphos to C−O Activation in the Presence of Nucleophilic Metal Hydrides

C−O bond activation of DPEphos occurs upon mild heating in the presence of [Ru(NHC)(2)(PPh(3))(2)H(2)] (NHC=N‐heterocyclic carbene) to form phosphinophenolate products. When NHC=IEt(2)Me(2), C−O activation is accompanied by C−N activation of an NHC ligand to yield a coordinated N‐phosphino‐functionalised carbene. DFT calculations define a nucleophilic mechanism in which a hydride ligand attacks the aryl carbon of the DPEphos C−O bond. This is promoted by the strongly donating NHC ligands which render a trans dihydride intermediate featuring highly nucleophilic hydride ligands accessible. C−O bond activation also occurs upon heating cis‐[Ru(DPEphos)(2)H(2)]. DFT calculations suggest this reaction is promoted by the steric encumbrance associated with two bulky DPEphos ligands. Our observations that facile degradation of the DPEphos ligand via C−O bond activation is possible under relatively mild reaction conditions has potential ramifications for the use of this ligand in high‐temperature catalysis.