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Synthesis and Properties of Chiral Ruthenium Complexes Containing O ‐, S ‐ and P ‐Functionalized Cp‐Ligands
Author(s) -
van der Zeijden Adolphus A. H.,
Jimenez Jhonny,
Mattheis Chris,
Wagner Christoph,
Merzweiler Kurt
Publication year - 1999
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(199911)1999:11<1919::aid-ejic1919>3.0.co;2-6
Subject(s) - chemistry , denticity , ruthenium , diastereomer , ligand (biochemistry) , stereochemistry , medicinal chemistry , ether , lewis acids and bases , enantioselective synthesis , catalysis , organic chemistry , crystal structure , biochemistry , receptor
Novel, functionalized, chiral Cp‐ligands with S‐ and P‐donor atoms were designed. Together with known analogues containing ether side‐chains they were complexed to ruthenium for use as chiral Lewis‐acid catalysts. In the ether complexes [RuCl(η 5 ‐C 5 H 4 CH 2 CH 2 OR)(PPh 3 ) 2 ] {R = Me, (1 S )‐isobornyl, (1 R )‐menthyl, (1 R )‐fenchyl} the Cp‐ligand is only η 5 ‐coordinated; all attempts to provoke a bidentate, Cp/O coordination were unsuccessful. The sulfide complex [Ru{η 5 :η 1 ‐C 5 H 4 CH 2 CH 2 S[(1 R )‐neomenthyl]}(PPh 3 ) 2 ][OTf] contains a bidentate Cp/S‐coordinated ligand, but it is unstable. The stable phosphane complex [RuCl(η 5 :η 1 ‐C 5 H 4 CH 2 CH(Me)PPh 2 )(PPh 3 )] exists as a 77:23 mixture of diastereomers containing a strongly bidentate Cp/P ligand. The diastereomers interchange, with Ru–Cl bond cleavage as the rate‐determining step.