2-(2-Pyridyl)-4,6-diphenylphosphinine versus 2-(2-Pyridyl)-4,6-diphenylpyridine : synthesis, characterization, and reactivity of cationic RhIII and IrIII complexes based on aromatic phosphorus heterocycles

I.M.J. Krom, de, L.E.E. Broeckx, M. Lutz, C. Müller

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

38 Citaten (Scopus)

Samenvatting

The bidentate P,N hybrid ligand 1 allows access for the first time to novel cationic phosphinine-based RhIII and IrIII complexes, broadening significantly the scope of low-coordinate aromatic phosphorus heterocycles for potential applications. The coordination chemistry of 1 towards RhIII and IrIII was investigated and compared with the analogous 2,2-bipyridine derivative, 2-(2-pyridyl)-4,6-diphenylpyridine (2), which showed significant differences. The molecular structures of [RhCl(Cp*)(1)]Cl and [IrCl(Cp*)(1)]Cl (Cp*=pentamethylcyclopentadienyl) were determined by means of X-ray diffraction and confirm the mononuclear nature of the 3-phosphinineRhIII and IrIII complexes. In contrast, a different reactivity and coordination behavior was found for the nitrogen analogue 2, especially towards RhIII as a bimetallic ion pair [RhCl(Cp*)(2)]+[RhCl3(Cp*)] is formed rather than a mononuclear coordination compound. [RhCl(Cp*)(1)]Cl and [IrCl(Cp*)(1)]Cl react with water regio- and diastereoselectively at the external PC double bond, leading exclusively to the anti-addition products [MCl(Cp*)(1HOH)]Cl as confirmed by X-ray crystal-structure determination.
Originele taal-2Engels
Pagina's (van-tot)3676-3684
Aantal pagina's9
TijdschriftChemistry : A European Journal
Volume19
Nummer van het tijdschrift11
DOI's
StatusGepubliceerd - 2013

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