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Structure, Stereochemistry and Dynamics of Tetranuclear Polyhydride Clusters Containing Chiral Heterobidentate Phosphanes
Author(s) -
Ponomarenko Vadim I.,
Krupenya Dmitrii V.,
Grachova Elena V.,
Gindin Vladimir A.,
Selivanov Stanislav I.,
Koshevoy Igor O.,
Tunik Sergey P.,
Haukka Matti,
Pursiainen Jouni,
Pirilä Päivi
Publication year - 2009
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200900259
Subject(s) - oxazoline , chemistry , diastereomer , moiety , stereoselectivity , stereochemistry , ligand (biochemistry) , isopropyl , ring (chemistry) , nitrogen atom , chelation , crystallography , medicinal chemistry , organic chemistry , catalysis , biochemistry , receptor
A novel chiral phosphane ( S )‐2‐(4‐isopropyl‐2‐oxazoline‐2‐yl)phenyl‐di‐ N ‐pyrrolylphosphane ( S‐ PyrPOx) based on asymmetric oxazoline ring has been prepared and characterised. Reaction of this ligand and its phenyl‐substituted analogue ( S‐ PhPOx) with H 4 Ru 4 (CO) 12 and H 3 RhOs 3 (CO) 12 gave substituted derivatives H 4 Ru 4 (CO) 10 (1,1‐PhPOx) ( 2 ), H 4 Ru 4 (CO) 10 (1,1‐PyrPOx) ( 3 ), and H 3 RhOs 3 (CO) 10 (1,1‐PyrPOx) ( 4 ), which were structurally characterised by X‐ray crystallography in solid state and by a variety of multinuclear NMR spectroscopic measurements in solution. In all studied clusters the coordinated ligands form five‐membered chelate rings through phosphorus and nitrogen atoms of oxazoline moiety to afford a novel chiral center associated with the substituted metal atom. The substitution reactions demonstrate extremely high stereoselectivity, which results in formation of only one diastereomer in all three cases to give S , S isomer in 2 and S , R isomer in 3 and 4 .