Amine olefin rhodium(i) complexes: pKaand NH bond strength
- 1 January 2004
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Chemical Communications
- No. 24,p. 2820-2821
- https://doi.org/10.1039/b409981h
Abstract
A combination of the rigid bis(5H-dibenzo[a,d]cyclohepten-5-yl)amine (trop2NH) and 5-amino-5H-dibenzo[a,d]cycloheptene (tropNH2) ligand allowed the synthesis of the stable pentacoordinated 18 electron amine olefin rhodium(I) complex [Rh(trop2NH)(tropNH2)]O3SCF3 (5); this complex can be cleanly deprotonated [pKa DMSO = 20.6(1)] to the corresponding amide [Rh(trop2N)(tropNH2)] (6) which is reversibly oxidised at −0.466 V (vs. Fc/Fc+). The coordinated NH bond strength in 5 is estimated to be 379 ± 10 kJ mol−1.Keywords
This publication has 18 references indexed in Scilit:
- Olefins as Steering Ligands for Homogeneously Catalyzed HydrogenationsChemistry – A European Journal, 2004
- Readily Available [2.2.2]-Bicyclooctadienes as New Chiral Ligands for Ir(I): Catalytic, Kinetic Resolution of Allyl CarbonatesJournal of the American Chemical Society, 2004
- A Chiral Chelating Diene as a New Type of Chiral Ligand for Transition Metal Catalysts: Its Preparation and Use for the Rhodium-Catalyzed Asymmetric 1,4-AdditionJournal of the American Chemical Society, 2003
- Iridium(I) versus Ruthenium(II). A Computational Study of the Transition Metal Catalyzed Transfer Hydrogenation of KetonesOrganometallics, 2003
- Aminosulf(ox)ides as Ligands for Iridium(I)-Catalyzed Asymmetric Transfer HydrogenationThe Journal of Organic Chemistry, 2000
- Structure of the Diamine−Rh(I) Precursor in the Asymmetric Hydride Transfer Reduction of Ketones: A Theoretical and Experimental ApproachJournal of the American Chemical Society, 1998
- Synthesis and characterization of rhodium complexes [Rh(Az)(L)Cl] (Az 2,2-dimethyl-3-phenyl-3-allylaziridine; L C2H4, CO, orJournal of Organometallic Chemistry, 1992
- Metallkomplexe mit biologisch wichtigen liganden LVI. Darstellung, struktur und reaktionen von C-allylglycin-rhodium- und -iridium-komplexenJournal of Organometallic Chemistry, 1990
- Optically active phenanthrolines in asymmetric catalysis. III. Highly efficient enantioselective transfer hydrogenation of acetophenone by chiral rhodium/3-alkyl phenanthroline catalysts.Tetrahedron: Asymmetry, 1990
- Synthesis and characterization of rhodium(I) amino olefin complexesOrganometallics, 1988