Stereoselective formation of (aminoalkyl)platinum complexes from imines

Citation
Cr. Baar et al., Stereoselective formation of (aminoalkyl)platinum complexes from imines, ORGANOMETAL, 20(3), 2001, pp. 408-417
Citations number
56
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANOMETALLICS
ISSN journal
0276-7333 → ACNP
Volume
20
Issue
3
Year of publication
2001
Pages
408 - 417
Database
ISI
SICI code
0276-7333(20010205)20:3<408:SFO(CF>2.0.ZU;2-M
Abstract
Reaction of [PtMe2(mu -SMe2)](2) with cis-1,2-C6H10(N=CH-2-C5H4N)(2) (1) an d cis-1,2-C6H10-(N=CH-2-C9H6-N)(2) (2) gives the complexes [PtMe2{cis-1,2-C 6H10(N=CH-2-C5H4N)(2)}] (3) and [PtMe2{cis-1,2-C6H10(N=CH-2-C9H6N)(2)}] (4) , respectively (C5H4N = pyridyl; C9H6N = quinolyl), in which the ligand is bidentate such that each complex is chiral and contains a free imine substi tuent. Complexes 3 and 4 react with protic acids, HCl and CF3CO2H, to form (aminoalkyl)platinum(IV) products that contain a new asymmetric carbon cent er, often with very high stereoselectivity. In these products the complex l igand may act as a tridentate N,N,C donor or, in complexes containing an az aplatinacyclobutane ring, as a tetradentate N,N,N,C donor. The absolute con figurations of five (aminoalkyl)platinum(IV) products were determined by X- ray crystal structure determinations and gave a benchmark such that the ste reochemistries of other complexes could be assigned by NMR. It is suggested that the reactions occur by protonation at the free imine nitrogen to give an iminium ion, and the carbocation then adds to the adjacent platinum(II) center. The initially formed products may rearrange by mechanisms involvin g reversible ligand dissociation from platinum(IV) or deprotonation of the aminoalkyl group.