Unexpected Vulnerability of DPEphos to C-O Activation in the Presence of Nucleophilic Metal Hydrides.
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ABSTRACT: C-O bond activation of DPEphos occurs upon mild heating in the presence of [Ru(NHC)2 (PPh3 )2 H2 ] (NHC=N-heterocyclic carbene) to form phosphinophenolate products. When NHC=IEt2 Me2 , 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 H2 ]. DFT calculations suggest this reaction is promoted by
SUBMITTER: Cybulski MK
PROVIDER: S-EPMC7496192 | biostudies-literature | 2020 Sep
REPOSITORIES: biostudies-literature
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