Dissimilarity in the Chemical Behavior of Osmaoxazolium Salts and Osmaoxazoles: Two Different Aromatic Metalladiheterocycles

Overview

Journal Organometallics

Publisher American Chemical Society

Date 2022 Mar 10

PMID 35264819

Authors

Maria L Buil

Miguel A Esteruelas

Enrique Onate

Nieves R Picazo

Affiliations

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Abstract

The preparation of aromatic hydride-osmaoxazolium and hydride-oxazole compounds is reported and their reactivity toward phenylacetylene investigated. Complex [OsH(OH)(≡CPh)(IPr)(PPr)]OTf (; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene, OTf = CFSO) reacts with acetonitrile and benzonitrile to give [OsH{κ--[C(Ph)NHC(R)O]}(NCR)(IPr)(PPr)]OTf (R = Me (), Ph ()) via amidate intermediates, which are generated by addition of the hydroxide ligand to the nitrile. In agreement with this, the addition of 2-phenylacetamide to acetonitrile solutions of gives [OsH{κ--[C(Ph)NHC(CHPh)O]}(NCCH)(IPr)(PPr)]OTf (). The deprotonation of the osmaoxazolium ring of and leads to the oxazole derivatives OsH{κ--[C(Ph)NC(R)O]}(IPr)(PPr) (R = Me (), CHPh ()). Complexes and add their Os-H and Os-C bonds to the C-C triple bond of phenylacetylene to afford [Os{η- κ--[CHC(Ph)C(Ph)NHC(R)O]}(NCCH)(IPr)]OTf (R = Me (), CHPh ()), bearing a tridentate amide-N-functionalized allyl ligand, while complexes and undergo a vicarious nucleophilic substitution of the hydride at the metal center with the alkyne, via the compressed dihydride adduct intermediates OsH(C≡CPh){κ--[C(Ph)NC(R)O]}(IPr)(PPr) (R = Me (), CHPh ()), which reductively eliminate H to yield the acetylide-osmaoxazoles Os(C≡CPh){κ--[C(Ph)NC(R)O]}(IPr)(PPr) (R = Me (), CHPh ()).

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