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Unusual Crystal Structures of ( R Ru R C / S Ru R C )‐(η 6 ‐ p ‐Cymene)Ru Complexes – Diastereomers with Opposite Configuration at the Metal Center in the Unit Cell
Author(s) -
Brunner Henri,
Neuhierl Thomas,
Nuber Bernhard
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(199812)1998:12<1877::aid-ejic1877>3.0.co;2-e
Subject(s) - chemistry , diastereomer , ruthenium , stereochemistry , benzene , ligand (biochemistry) , intramolecular force , metal , center (category theory) , crystal structure , medicinal chemistry , crystallography , catalysis , organic chemistry , biochemistry , receptor
Condensation of ( R )‐2‐aminobutanol with salicylaldehyde and 2‐pyrrolecarbaldehyde gave the chiral chelate ligands HLL 1 * and HLL 2 *, respectively. The diastereomeric complexes ( R Ru , R C )‐ and ( S Ru , R C )‐[(η 6 ‐arene)Ru(LL 1 *)Cl], η 6 ‐arene = p ‐cymene ( 1a / 1b ), η 6 ‐arene = benzene ( 2a / 2b ), and ( R Ru , R C )‐ and ( S Ru , R C )‐[(η 6 ‐arene)Ru(LL 2 *)Cl], η 6 ‐arene = p ‐cymene ( 3a / 3b ), η 6 ‐arene = benzene ( 4a / 4b ), which only differ in the ruthenium configuration, were prepared by the reaction of [(η 6 ‐arene)RuCl 2 ] 2 with the anion of the corresponding ligand HLL*. X‐ray analyses of 1a / 1b and 3a / 3b showed a structural peculiarity. The unit cell of these complexes contained diastereomers with the same configuration at the carbon atoms but opposite configuration at the metal centers in a 1:1 ratio. Weak intramolecular O–H···Cl hydrogen bridges were formed in all the complexes. 1 H‐NMR studies demonstrated the configurational lability at the Ru center. The iodo complexes ( R Ru , R C )‐ and ( S Ru , R C )‐[(η 6 ‐ p ‐cymene)Ru(LL*)I], LL* = LL 1 * ( 5a / 5b ) and LL* = LL 2 * ( 6a / 6b ), were synthesized by halogen exchange.