Jump to main content
Jump to site search

Issue 3, 2018
Previous Article Next Article

High-valent nitridorhenium(V) complexes containing PNP ligands: implications of ligand flexibility

Author affiliations

Abstract

The synthesis of (PNP)Re(N)X (PNP = [2-P(CHMe2)2-4-MeC6H3]2N, X = Cl and Me) complexes is described. The methylnitridorhenium complex 3 was found to react differently with CO and isocyanides, leading to the isolation of a Re(V) acyl complex 4 and an isocyanide adduct 6. Two parallel pathways were observed for the reaction of 3 with CO: (1) CO inserts into the Re–Me bond to afford 4, and (2) 3 isomerizes by distortion of the aryl backbone of the PNP ligand to afford the isomer 3′. This is followed by the reaction of 3′ with CO to afford the tricarbonyl complex 5, which was fully characterized. The contrasting reaction of 3 with 2,6-dimethylphenyl isocyanide lends further support for the proposed isomerization pathway. DFT (M06) calculations suggest that insertion of CNR into the Re–Me bond (27.2 kcal mol−1) is inaccessible at room temperature. Instead the substrate adds to the metal center via the most accessible face i.e. syn to the rhenium–nitrido bond, to afford 6. The addition of CO to isomer 3′ is proposed to proceed with a similar mechanism to 2,6-dimethylphenyl isocyanide.

Graphical abstract: High-valent nitridorhenium(v) complexes containing PNP ligands: implications of ligand flexibility

Back to tab navigation

Supplementary files

Publication details

The article was received on 25 Sep 2017, accepted on 07 Dec 2017 and first published on 08 Dec 2017


Article type: Paper
DOI: 10.1039/C7DT03615A
Citation: Dalton Trans., 2018,47, 758-768
  •   Request permissions

    High-valent nitridorhenium(V) complexes containing PNP ligands: implications of ligand flexibility

    N. S. Lambic, R. D. Sommer and E. A. Ison, Dalton Trans., 2018, 47, 758
    DOI: 10.1039/C7DT03615A

Search articles by author

Spotlight

Advertisements