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Crystallization‐Induced Asymmetric Transformation of Chiral‐at‐metal Ruthenium( II ) Complexes Bearing Achiral Ligands
Author(s) -
Hamelin Olivier,
Pécaut Jacques,
Fontecave Marc
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305749
Subject(s) - enantiopure drug , ruthenium , chemistry , enantiomer , diimine , crystallization , stereoselectivity , ligand (biochemistry) , racemic mixture , medicinal chemistry , diastereomer , chiral resolution , stereochemistry , oxazoline , enantioselective synthesis , organic chemistry , catalysis , receptor , biochemistry
Recently, we observed that the enantiopure Λ form of the tributylammonium salt of the chiral anion tris[tetrachlorobenzene‐1,2‐bis(olato)]phosphate, also named Trisphat, was able to induce an efficient resolution of a Δ,Λ racemic mixture of cis ‐[Ru(dmp) 2 (NCCH 3 ) 2 ](PF 6 ) 2 (dmp=2,9‐dimethyl‐1,10‐phenanthroline) due to the spontaneous and selective precipitation of the heterochiral pair [Δ‐Ru(dmp) 2 (CH 3 CN) 2 ][Λ‐Trisphat] 2 . We report here that the combination of such a stereoselective precipitation process and irradiation results in the quantitative conversion of the initial [Ru(dmp) 2 (NCCH 3 ) 2 ] 2+ racemate into only one of the two enantiomers. This is the first example in inorganic chemistry of an asymmetric transformation that leads to a chiral complex with no chiral ligand. Finally, three new racemic ruthenium bis(diimine) complexes, namely [Ru(dmp) 2 (NCCH 3 )Py](PF 6 ) 2 (Py=pyridine), [Ru(dmp) 2 (1,3‐diaminopropane)](PF 6 ) 2 , and [Ru(dmp) 2 (ethylenediamine)](PF 6 ) 2 were synthesized. For all of them, crystallization‐induced asymmetric transformation proved to be an efficient way of obtaining the corresponding optically active chiral‐at‐metal complexes in high yields and with excellent stereoselectivities.