Relevant stereochemical and coordination features of 1,3,5,7-tetramethyl-2,6,9-trioxo-bicyclo[3,3,1]nona-3,7-diene (TOND), a chiral molecule of C-2 symmetry are described. The X-ray crystal structure of [RhCl{(S)-CHPhMeNH2}{(+)-TOND}] has ascertained that the absolute configuration of (+)-TOND is R,R. Furthermore, the synthesis of stable cationic Pd(II) pi-allyl complexes of general formula [Pd(eta(3)-allyl)(TOND)][BF4] has allowed to probe the ability of this ligand to afford stereoselective coordination of prochiral fragments. The X-ray molecular structure of the representative compound [Pd(eta(3)-crotyl)(TOND)][BF4] has been determined. Finally, the influence of TOND on the stereochemistry of prochiral nitrogen donors of diamine and phosphamine chelates has been explored in rhodium complexes of general formula [Rh(chelate)(TOND)][BF4]. The configurations of the nitrogen donors have resulted as stereospecifically selected by the presence of TOND. (C) 2003 Elsevier B.V. All rights reserved.
Absolute configuration, coordination and stereochemical influence of 1,3,5,7-tetramethyl-2,6,9-trioxo-bicyclo[3,3,1]nona-3,7-diene in Rh(I) and cationic Pd(II) complexes
ROVIELLO, Giuseppina;
2003-01-01
Abstract
Relevant stereochemical and coordination features of 1,3,5,7-tetramethyl-2,6,9-trioxo-bicyclo[3,3,1]nona-3,7-diene (TOND), a chiral molecule of C-2 symmetry are described. The X-ray crystal structure of [RhCl{(S)-CHPhMeNH2}{(+)-TOND}] has ascertained that the absolute configuration of (+)-TOND is R,R. Furthermore, the synthesis of stable cationic Pd(II) pi-allyl complexes of general formula [Pd(eta(3)-allyl)(TOND)][BF4] has allowed to probe the ability of this ligand to afford stereoselective coordination of prochiral fragments. The X-ray molecular structure of the representative compound [Pd(eta(3)-crotyl)(TOND)][BF4] has been determined. Finally, the influence of TOND on the stereochemistry of prochiral nitrogen donors of diamine and phosphamine chelates has been explored in rhodium complexes of general formula [Rh(chelate)(TOND)][BF4]. The configurations of the nitrogen donors have resulted as stereospecifically selected by the presence of TOND. (C) 2003 Elsevier B.V. All rights reserved.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
