Monohydride-Dichloro Rhodium(III) Complexes with Chiral Diphosphine Ligands as Catalysts for Asymmetric Hydrogenation of Olefinic Substrates
- Journal Article
We report full details of the synthesis and characterization of monohydride‐dichloro rhodium(III) complexes bearing chiral diphosphine ligands, such as (S )‐BINAP, (S )‐DM‐SEGPHOS, and (S )‐DTBM‐SEGPHOS, producing cationic triply chloride bridged dinuclear rhodium(III) complexes (1 a : (S )‐BINAP; 1 b : (S )‐DM‐SEGPHOS) and a neutral mononuclear monohydride‐dichloro rhodium(III) complex (1 c : (S )‐DTBM‐SEGPHOS) in high yield and high purity. Their solid state structure and solution behavior were determined by crystallographic studies as well as full spectral data, including DOSY NMR spectroscopy. Among these three complexes, 1 c has a rigid pocket surrounded by two chloride atoms bound to the rhodium atom together with one t Bu group of (S )‐DTBM‐SEGPHOS for fitting to simple olefins without any coordinating functional groups. Complex 1 c exhibited superior catalytic activity and enantioselectivity for asymmetric hydrogenation of exo‐olefins and olefinic substrates. The catalytic activity of 1 c was compared with that of well‐demonstrated dihydride species derived in situ from rhodium(I) precursors such as [Rh(cod)Cl]2 and [Rh(cod)2]+[BF4]− upon mixing with (S )‐DTBM‐SEGPHOS under dihydrogen. © Wiley 2020 Show more
Journal / seriesChemistry - A European Journal
Pages / Article No.
Subjectasymmetric hydrogenation; monohydride; mononuclear complexes; rhodium; simple olefins
Organisational unit03363 - Togni, Antonio (emeritus) / Togni, Antonio (emeritus)
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