Impact of Na- and K-C pi-interactions on the structure and binding of M3(sol)n(BINOLate)3Ln catalysts.
Shibasaki's heterobimetallic complexes M3(THF)n(BINOLate)3Ln [M = Li, Na, K; Ln = lanthanide(III)] are among the most successful asymmetric Lewis acid catalysts. Why does M3(THF)n(BINOLate)3Ln readily bind substrates when M = Li but not when M = Na or K? Structural studies herein indicate Na- and K-C cation-pi interactions and alkali metal radius may be more important than even lanthanide radius. Also reported is a novel polymeric [K3(THF)2(BINOLate)3Yb]n structure that provides the first evidence of interactions between M3(THF)n(BINOLate)3Ln complexes.
P. Roy and Diana T. Vagelos Laboratories, University of Pennsylvania, Department of Chemistry, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
Alfred J
AJ
Wooten
Patrick J
PJ
Carroll
Patrick J
PJ
Walsh
D001665:Binding Sites; D002384:Catalysis; D004583:Electrons; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008094:Lithium; D008672:Metals, Alkali / Q000138:chemical synthesis*; D015394:Molecular Structure; D009284:Naphthols / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis*; D011188:Potassium; D012964:Sodium; D013763:Tetrahydrofolates / Q000737:chemistry*
C406944:BINOL, naphthol; D028581:Lanthanoid Series Elements; D008672:Metals, Alkali; D009284:Naphthols; D009942:Organometallic Compounds; D013763:Tetrahydrofolates; C030371:5,6,7,8-tetrahydrofolic acid; D008094:Lithium; D012964:Sodium; D011188:Potassium