Formation of Trinuclear Rhodium-Hydride Complexes [{Rh(PP*)H}3- (μ2-H)3(μ3-H)][anion]2-During Asymmetric Hydrogenation?

Autor:	Kohrt, C., Baumann, W., Spannenberg, A., Drexler, H.‐J., Gridnev, I. D., Heller, D.
Předmět:	HYDRIDES REACTION mechanisms (Chemistry) RHODIUM HYDROGENATION DIPHOSPHINE CHELATION DIOLEFINS CYCLOOCTADIENE
Zdroj:	Chemistry - A European Journal; Jun2013, Vol. 19 Issue 23, p7443-7451, 9p
Abstrakt:	Recently described and fully characterized trinuclear rhodium-hydride complexes [{Rh(PP*)H}3(μ2-H)3(μ3-H)][anion]2 have been investigated with respect to their formation and role under the conditions of asymmetric hydrogenation. Catalyst-substrate complexes with mac (methyl ( Z)- N-acetylaminocinnamate) ([Rh( tBu-BisP*)(mac)]BF4, [Rh(Tangphos)(mac)]BF4, [Rh(Me-BPE)(mac)]BF4, [Rh(DCPE)(mac)]BF4, [Rh(DCPB)(mac)]BF4), as well as rhodium-hydride species, both mono-([Rh(Tangphos)- H2(MeOH)2]BF4, [Rh(Me-BPE)H2(MeOH)2]BF4), and dinuclear ([{Rh(DCPE)H}2(μ2-H)3]BF4, [{Rh(DCPB)H}2(μ2-H)3]BF4), are described. A plausible reaction sequence for the formation of the trinuclear rhodium-hydride complexes is discussed. Evidence is provided that the presence of multinuclear rhodium-hydride complexes should be taken into account when discussing the mechanism of rhodium-promoted asymmetric hydrogenation. [ABSTRACT FROM AUTHOR]
Databáze:	Complementary Index
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