TY - JOUR
T1 - Chiral induction at octahedral Ru(II) via the disassembly of diruthenium(II,III) tetracarboxylates using a variety of chiral diphosphine ligands
AU - Groves, Brandon R.
AU - Arbuckle, D. Ian
AU - Essoun, Ernest
AU - Lundrigan, Travis L.
AU - Wang, Ruiyao
AU - Aquino, Manuel A.S.
PY - 2013/10/7
Y1 - 2013/10/7
N2 - Achiral [Ru2(μ-O2CR)4(MeOH) 2](PF6) (R = CH3 or C6H5) reacts with the chiral diphosphines R,R- and S,S-Chiraphos (two chiral centers on ligand between the coordinating P atoms) and R-Prophos (one chiral center on ligand between the coordinating P atoms) leading to a disassembly of the paddlewheel core and the highly diastereoselective production of Λ-[Ru(η2-O2CC6H5) (η2-R,R-Chiraphos)2](PF6) (Λ-R,R-III), Δ-[Ru(η2-O2CC 6H5)(η2-S,S-Chiraphos)2](PF 6) (Δ-S,S-III) (the R = CH3 complexes of Chiraphos were reported in a earlier communication in this journal), and Λ-[Ru(η2-O2CCH3)(η2- R-Prophos)2](PF6) (Λ-R,R-VI), respectively, in high yield and purity. Reactions of the same starting material with R,R- and S,S-o-tolyl-Dipamp (chiral centers are the coordinating P-atoms) lead to an inversion in the chirality-at-metal producing Λ-[Ru(η2- O2CC6H5)(η2-S,S-o-tolyl-Dipamp) 2](PF6) (Λ-S,S-IV), Δ-[Ru(η2- O2CC6H5)(η2-R,R-o-tolyl-Dipamp) 2](PF6) (Δ-R,R-IV), Λ-[Ru(η2- O2CCH3)(η2-S,S-o-tolyl-Dipamp) 2](PF6) (Λ-S,S-V), and Δ- [Ru(η2-O2CCH3)(η2-R,R-o- tolyl-Dipamp)2](PF6) (Δ-R,R-V). X-ray crystallography of all but Λ-S,S-V and Δ-R,R-V and solid-state circular dichroism (CD) show that only the indicated diastereomers are present in the solid-state. Solution CD measurements and 31P NMR also indicate their predominance in solution.
AB - Achiral [Ru2(μ-O2CR)4(MeOH) 2](PF6) (R = CH3 or C6H5) reacts with the chiral diphosphines R,R- and S,S-Chiraphos (two chiral centers on ligand between the coordinating P atoms) and R-Prophos (one chiral center on ligand between the coordinating P atoms) leading to a disassembly of the paddlewheel core and the highly diastereoselective production of Λ-[Ru(η2-O2CC6H5) (η2-R,R-Chiraphos)2](PF6) (Λ-R,R-III), Δ-[Ru(η2-O2CC 6H5)(η2-S,S-Chiraphos)2](PF 6) (Δ-S,S-III) (the R = CH3 complexes of Chiraphos were reported in a earlier communication in this journal), and Λ-[Ru(η2-O2CCH3)(η2- R-Prophos)2](PF6) (Λ-R,R-VI), respectively, in high yield and purity. Reactions of the same starting material with R,R- and S,S-o-tolyl-Dipamp (chiral centers are the coordinating P-atoms) lead to an inversion in the chirality-at-metal producing Λ-[Ru(η2- O2CC6H5)(η2-S,S-o-tolyl-Dipamp) 2](PF6) (Λ-S,S-IV), Δ-[Ru(η2- O2CC6H5)(η2-R,R-o-tolyl-Dipamp) 2](PF6) (Δ-R,R-IV), Λ-[Ru(η2- O2CCH3)(η2-S,S-o-tolyl-Dipamp) 2](PF6) (Λ-S,S-V), and Δ- [Ru(η2-O2CCH3)(η2-R,R-o- tolyl-Dipamp)2](PF6) (Δ-R,R-V). X-ray crystallography of all but Λ-S,S-V and Δ-R,R-V and solid-state circular dichroism (CD) show that only the indicated diastereomers are present in the solid-state. Solution CD measurements and 31P NMR also indicate their predominance in solution.
UR - http://www.scopus.com/inward/record.url?scp=84885106167&partnerID=8YFLogxK
U2 - 10.1021/ic401908t
DO - 10.1021/ic401908t
M3 - Article
AN - SCOPUS:84885106167
SN - 0020-1669
VL - 52
SP - 11563
EP - 11572
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 19
ER -