Premium
Chiral Ruthenium–Allenylidene Complexes That Bear a Fullerene Cyclopentadienyl Ligand: Synthesis, Characterization, and Remote Chirality Transfer
Author(s) -
Zhong YuWu,
Matsuo Yutaka,
Nakamura Eiichi
Publication year - 2007
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200600341
Subject(s) - ruthenium , chirality (physics) , ligand (biochemistry) , propargyl alcohol , cyclopentadienyl complex , chemistry , electrophile , nucleophile , fullerene , medicinal chemistry , photochemistry , catalysis , organic chemistry , biochemistry , chiral symmetry breaking , physics , receptor , quantum mechanics , nambu–jona lasinio model , quark
Ruthenium complexes that bear both a fullerene and an allenylidene ligand, [Ru(C 60 Me 5 )(( R )‐prophos)=CCCR 1 R 2 ]PF 6 (prophos=1,2‐bis(diphenylphosphanyl)propane), were prepared by the reaction of [Ru(C 60 Me 5 )Cl(( R )‐prophos)] and a propargyl alcohol in better than 90 % yields, and characterized by 1 H, 13 C, and 31 P NMR, IR, and UV/Vis/NIR spectroscopy and MS. Cyclic voltammograms of these complexes showed one reversible or irreversible reduction wave due to the allenylidene part, and two reversible reduction waves due to the fullerene core. Nucleophilic addition of RMgBr or RLi proceeded regioselectively at the distal carbon atom of the allenylidene array. The reaction took place with a 60:40–95:5 level of diastereoselectivity with respect to the original chirality in the ( R )‐prophos ligand, which is located six atoms away from the electrophilic carbon center.