Premium
Isolation of Enantiomers of a Range of Tris(bidentate)ruthenium(II) Species Using Chromatographic Resolution and Stereoretentive Synthetic Methods
Author(s) -
Rutherford Todd J.,
Pellegrini Paul A.,
AldrichWright Janice,
Junk Peter C.,
Keene F. Richard
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199811)1998:11<1677::aid-ejic1677>3.0.co;2-s
Subject(s) - chemistry , ruthenium , homoleptic , denticity , quinoxaline , enantiomer , phenazine , ligand (biochemistry) , chiral resolution , decarbonylation , tartrate , tris , medicinal chemistry , stereochemistry , crystallography , inorganic chemistry , organic chemistry , crystal structure , metal , biochemistry , receptor , catalysis
A range of chiral building blocks of the type Δ‐ or Λ‐[Ru(pp) 2 (CO) 2 ] 2+ {pp = bidentate ligands bpy (2,2′‐bipyridine), phen (1,10‐phenanthroline) and Me 2 bpy (4,4′‐dimethyl‐2,2′‐bipyridine)} have been synthesized, and their enantiomeric purity and absolute configurations determined by CD and NMR studies. Decarbonylation using trimethylamine oxide in the presence of the respective pp ligand at room temperature produced the corresponding tris(bidentate) species [Ru(pp) 3 ] 2+ with retention of configuration at the ruthenium(II) centre. A general chromatographic technique for resolution of tris‐homoleptic complexes of the type [Ru(pp) 3 ] 2+ was investigated, with the absolute configurations of the resolved complexes confirmed by CD studies, and the X‐ray structural analyses of Δ‐(–)‐[Ru(Me 2 bpy) 3 ]{(–)‐ O,O′ ‐dibenzoyl‐ L ‐tartrate} and Λ‐(+)‐[Ru(phen) 3 ]{(+)‐ O,O′ ‐di‐4‐toluoyl‐ D ‐tartrate}. Resolution is also reported for the analogous species containing three potential bridging ligands, [Ru(bpm) 3 ] 2+ and [Ru(HAT) 3 ] 2+ (bpm = 2,2′‐bipyrimidine; HAT = 1,4,5,8,9,12‐hexaazatriphenylene). The versatility of the chromatographic procedure was demonstrated by the resolution of a series of bis‐heteroleptic complexes [Ru(pp) 2 (pp′)] 2+ {pp′ = dpq (dipyrido[3,2‐ d :2,3′‐ f ]quinoxaline), dpqc (dipyrido[3,2‐ a :2,3‐ d ]‐6,7,8,9‐tetrahydrophenazine), and dppz {dipyrido[3,2‐ a :2,3′‐ d ]phenazine)}.