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2-(2'-Pyridyl)-4,6-diphenylphosphinine versus 2-(2'-pyridyl)-4,6-diphenylpyridine: synthesis, characterization, and reactivity of cationic Rh(III) and Ir(III) complexes based on aromatic phosphorus heterocycles.
Chemistry. 2013 Mar 11; 19(11):3676-84.C

Abstract

The bidentate P,N hybrid ligand 1 allows access for the first time to novel cationic phosphinine-based Rh(III) and Ir(III) complexes, broadening significantly the scope of low-coordinate aromatic phosphorus heterocycles for potential applications. The coordination chemistry of 1 towards Rh(III) and Ir(III) 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 λ(3) -phosphinine-Rh(III) and Ir(III) complexes. In contrast, a different reactivity and coordination behavior was found for the nitrogen analogue 2, especially towards Rh(III) 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 PC double bond, leading exclusively to the anti-addition products [MCl(Cp*)(1H⋅OH)]Cl as confirmed by X-ray crystal-structure determination.

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Publisher Full Text (DOI)

Authors+Show Affiliations

de Krom I
Chemical Engineering and Chemistry, Eindhoven University of Technology, Den Dolech 2, 5600 MB Eindhoven, The Netherlands.
Broeckx LE
No affiliation info available
Lutz M
No affiliation info available
Müller C
No affiliation info available

MeSH

CationsCrystallography, X-RayHeterocyclic CompoundsIridiumModels, MolecularMolecular StructureOrganometallic CompoundsOrganophosphorus CompoundsPhosphinesPyridinesRhodium

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

23361944

Citation

de Krom, Iris, et al. "2-(2'-Pyridyl)-4,6-diphenylphosphinine Versus 2-(2'-pyridyl)-4,6-diphenylpyridine: Synthesis, Characterization, and Reactivity of Cationic Rh(III) and Ir(III) Complexes Based On Aromatic Phosphorus Heterocycles." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 19, no. 11, 2013, pp. 3676-84.
de Krom I, Broeckx LE, Lutz M, et al. 2-(2'-Pyridyl)-4,6-diphenylphosphinine versus 2-(2'-pyridyl)-4,6-diphenylpyridine: synthesis, characterization, and reactivity of cationic Rh(III) and Ir(III) complexes based on aromatic phosphorus heterocycles. Chemistry. 2013;19(11):3676-84.
de Krom, I., Broeckx, L. E., Lutz, M., & Müller, C. (2013). 2-(2'-Pyridyl)-4,6-diphenylphosphinine versus 2-(2'-pyridyl)-4,6-diphenylpyridine: synthesis, characterization, and reactivity of cationic Rh(III) and Ir(III) complexes based on aromatic phosphorus heterocycles. Chemistry (Weinheim an Der Bergstrasse, Germany), 19(11), 3676-84. https://doi.org/10.1002/chem.201203621
de Krom I, et al. 2-(2'-Pyridyl)-4,6-diphenylphosphinine Versus 2-(2'-pyridyl)-4,6-diphenylpyridine: Synthesis, Characterization, and Reactivity of Cationic Rh(III) and Ir(III) Complexes Based On Aromatic Phosphorus Heterocycles. Chemistry. 2013 Mar 11;19(11):3676-84. PubMed PMID: 23361944.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - 2-(2'-Pyridyl)-4,6-diphenylphosphinine versus 2-(2'-pyridyl)-4,6-diphenylpyridine: synthesis, characterization, and reactivity of cationic Rh(III) and Ir(III) complexes based on aromatic phosphorus heterocycles. AU - de Krom,Iris, AU - Broeckx,Leen E E, AU - Lutz,Martin, AU - Müller,Christian, Y1 - 2013/01/29/ PY - 2012/10/10/received PY - 2013/1/31/entrez PY - 2013/1/31/pubmed PY - 2013/8/21/medline SP - 3676 EP - 84 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 19 IS - 11 N2 - The bidentate P,N hybrid ligand 1 allows access for the first time to novel cationic phosphinine-based Rh(III) and Ir(III) complexes, broadening significantly the scope of low-coordinate aromatic phosphorus heterocycles for potential applications. The coordination chemistry of 1 towards Rh(III) and Ir(III) 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 λ(3) -phosphinine-Rh(III) and Ir(III) complexes. In contrast, a different reactivity and coordination behavior was found for the nitrogen analogue 2, especially towards Rh(III) 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 PC double bond, leading exclusively to the anti-addition products [MCl(Cp*)(1H⋅OH)]Cl as confirmed by X-ray crystal-structure determination. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/23361944/2__2'_Pyridyl__46_diphenylphosphinine_versus_2__2'_pyridyl__46_diphenylpyridine:_synthesis_characterization_and_reactivity_of_cationic_Rh_III__and_Ir_III__complexes_based_on_aromatic_phosphorus_heterocycles_ L2 - https://doi.org/10.1002/chem.201203621 DB - PRIME DP - Unbound Medicine ER -