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

Cecilia Mariel Gallego, Carina Gaviglio, Yehoshoa Ben-David, David Milstein, Fabio Doctorovich, Juan Pellegrino

Research output: Contribution to journalArticle

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)]• (3•) was also carried out. Complex (3•) 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.

Original languageEnglish
Pages (from-to)7093-7108
Number of pages16
JournalDalton Transactions
Volume49
Issue number21
DOIs
Publication statusPublished - Jun 7 2020

ASJC Scopus subject areas

  • Inorganic Chemistry

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    Gallego, C. M., Gaviglio, C., Ben-David, Y., Milstein, D., Doctorovich, F., & Pellegrino, J. (2020). Synthesis, structure and reactivity of NO+, NO• and NO-pincer PCN-Rh complexes. Dalton Transactions, 49(21), 7093-7108. https://doi.org/10.1039/d0dt00962h