Issue 15, 2023

Phenylimido complexes of rhenium: fluorine substituents provide protection, reactivity, and solubility

Abstract

Reactions of [Re(NPhF)Cl3(PPh3)2] ({NPhF}2− = p-fluorophenylimide) with a variety of alkyl and aryl isocyanides have been studied. Different reactivity patterns and products have been obtained depending on the steric and electronic properties of the individual ligands. This involves the formation of 1 : 1 and 1 : 2 exchange products of Re(V) with the general formulae mer-[Re(NPhF)Cl3(PPh3)(isocyanide)] and cis- or trans-[Re(NPhF)Cl3(isocyanide)2]. The stability of the obtained products is correlated with the substitution pattern of the isocyanide ligands. The products have been studied by single-crystal X-ray diffraction and spectroscopic methods, including IR and multinuclear NMR spectroscopy as well as mass spectrometry. The use of partially fluorinated starting materials and ligands allows the modulation of the solubilities of the starting materials and the products as well as the monitoring of the reactions by means of 19F NMR. The attachment of the CF3 or F substituent on the isocyanides gives control over the steric bulk and the electronic properties of the ligands and, thus, their reactivity.

Graphical abstract: Phenylimido complexes of rhenium: fluorine substituents provide protection, reactivity, and solubility

Supplementary files

Article information

Article type
Paper
Submitted
11 Şub 2023
Accepted
07 Mar 2023
First published
08 Mar 2023
This article is Open Access
Creative Commons BY license

Dalton Trans., 2023,52, 4768-4778

Phenylimido complexes of rhenium: fluorine substituents provide protection, reactivity, and solubility

G. Claude, E. Kulitzki, A. Hagenbach, M. Roca Jungfer, J. S. Figueroa and U. Abram, Dalton Trans., 2023, 52, 4768 DOI: 10.1039/D3DT00446E

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