Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 21, 2020
Previous Article Next Article

Synthesis, structure and reactivity of NO+, NO˙ and NO pincer PCN-Rh complexes

Author affiliations

Abstract

Synthesis of a pincer-type linear nitrosyl complex [Rh(PtBu2CNEt2)(NO)]+ (3+) is described. The product and all intermediates involved were fully characterized by FTIR, NMR, cyclic voltammetry and X-ray crystallography. Attempts at obtaining (3+) from its chlorinated precursor Rh(PCN)(NO)Cl (2) revealed that a relative stabilization of this complex ion is introduced by the BArF counteranion, as other counteranions—PF6, BF4 and triflate—proved to coordinate to the metal center. Redox reactivity both of (3+) and of that of its five-coordinate derivatives (2) and [Rh(PCN)(NO)(CH3CN)]+ (4+) was found to distinguish itself from analogous PCP complexes due to a relative stabilization of higher oxidation states. Oxidation of these three complexes was studied by FTIR spectroelectrochemistry. Reduction of complex (3+) to yield a short-lived {RhNO}9 species [Rh(PCN)(NO)]˙ () was also carried out. Complex () was proved able to activate carbon–halogen bonds in aryl halides, in much a similar way as that of its PCP analogue. Complex (3+) was also seen to establish a linear ↔ bent nitrosyl equilibrium upon addition of CO which could not be fully displaced with excess CO.

Graphical abstract: Synthesis, structure and reactivity of NO+, NO˙ and NO− pincer PCN-Rh complexes

Back to tab navigation

Supplementary files

Article information


Submitted
13 Mar 2020
Accepted
04 May 2020
First published
04 May 2020

Dalton Trans., 2020,49, 7093-7108
Article type
Paper

Synthesis, structure and reactivity of NO+, NO˙ and NO pincer PCN-Rh complexes

C. M. Gallego, C. Gaviglio, Y. Ben-David, D. Milstein, F. Doctorovich and J. Pellegrino, Dalton Trans., 2020, 49, 7093
DOI: 10.1039/D0DT00962H

Social activity

Search articles by author

Spotlight

Advertisements