New chiral phosphoramidite allenylidene complexes of ruthenium obtained with chirality transfer

Facile one-pot access to a chiral at metal ruthenium pyrrolyl phosphine phosphoramidite complex

“…The 31 P NMR resonances for the phosphoramidite ligand 2a and the pyrrolyl ligand 1 appear at 170.7 and 124.8 ppm, respectively. Both values are in accordance with structurally related ruthenium PPyrl 3 [10b] and phosphoramidite complexes [4]. As observed in the NMR data, complex 5a was obtained as an optically pure single diastereomer,…”

“…These complexes are stereogenic at the metal and at the ligand, and thus form diastereomers, which can be separated by crystallization or column chromatography [4,5]. The optical purity of these diastereomeric metal complexes can be established by NMR spectroscopy, and in some cases one diastereomer is formed in excess [4,5].The ligand tri(N-pyrrolyl)phosphine (PPyrl 3 , 1) has recently gained considerable use in the synthesis of novel organometallic architectures [6]. Compared to other phosphorus based ligand systems, it exhibits increased π-acidity [7].…”

“…In previous research efforts, we have successfully accessed chiral at metal complexes employing chiral phosphoramidite ligands such as 2a ( Fig. 1) [4]. A thermal ligand exchange reaction from [RuCl(Ind) (PPh 3 ) 2 ] (3, Ind = η 5 -indenyl) afforded the complex [RuCl(Ind)(PPh 3 ) (2a)] (4, Fig.…”

Synthesis and Structural Characterization of a Series of New Chiral‐at‐Metal Ruthenium Allenylidene Complexes

“…These allenylidene complexes were obtained from the corresponding chiral‐at‐metal ruthenium chloro complexes with chirality transfer and are the first examples of allenylidene complexes with phosphoramidite ligands. A portion of this work has been communicated previously 27…”

Synthesis, Structural Characterization, and Catalytic Activity of Indenyl Tris(N‐pyrrolyl)phosphine Complexes of Ruthenium

“…The precursor complex [RuCl(ind)(PPh 3 ) 2 ] has been used as a starting material for the syntheses of ruthenium complex through ligand‐substitution reactions by us13,15e,15f and others 22. Accordingly, when [RuCl(ind)(PPh 3 ) 2 ] was heated with 1.1 equiv.…”