Dihydrogen-Bond-Promoted Catalysis: Catalytic Hydration of Nitriles with the Indenylruthenium Hydride Complex (η5-C9H7)Ru(dppm)H (dppm = Bis(diphenylphosphino)methane)
- 28 August 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (38) , 11539-11544
- https://doi.org/10.1021/ja034050q
Abstract
The indenylruthenium hydride complex (η5-C9H7)Ru(dppm)H was found to be active in catalyzing the hydration of nitriles to amides. The chloro analogue (η5-C9H7)Ru(dppm)Cl was, however, found to be inactive. Density functional theory calculations at the B3LYP level provide explanations for the effectiveness of the hydride complex and the ineffectiveness of the chloro complex in the catalysis. It is learned that the presence of a Ru−H···H−OH dihydrogen-bonding interaction in the transition state lowers the reaction barrier in the case of (η5-C9H7)Ru(dppm)H, but in the chloro system, the corresponding transition state does not contain this type of interaction and the reaction barrier is much higher. A similar dihydrogen-bond-promoting effect is believed to be responsible for the catalytic activity of the hydrotris(pyrazolyl)borato (Tp) ruthenium complex TpRu(PPh3)(CH3CN)H in CH3CN hydration. The chloro analogue TpRu(PPh3)(CH3CN)Cl shows no catalytic activity.This publication has 53 references indexed in Scilit:
- Promoting Effect of Water in Ruthenium-Catalyzed Hydrogenation of Carbon Dioxide to Formic AcidOrganometallics, 2001
- The catalytic hydration of nitriles to amides using a homogeneous platinum phosphinito catalystJournal of Molecular Catalysis A: Chemical, 2000
- Cooperative Binding of Nitrile Moieties Within a Bimetallic Pocket: Enforcing Side-On π-Interaction With a High-Spin Nickel(II) SiteEuropean Journal of Inorganic Chemistry, 2000
- Cooperative Transformations of Small Molecules at a Dinuclear Nickel(II) SiteChemistry – A European Journal, 1999
- Oxidative Addition of a Si−C(sp) Bond to Ruthenium: Synthesis and Reactivity of Ru(SiMe3)(C⋮CSiMe3)(CO)(PtBu2Me)2Organometallics, 1997
- Phosphine Substitution in Indenyl- and Cyclopentadienylruthenium Complexes. Effect of the η5 Ligand in a Dissociative PathwayOrganometallics, 1996
- Nitrile hydration catalysed by palladium(II) complexesJ. Chem. Soc., Dalton Trans., 1996
- Kinetics and mechanism of a cobalt(III) complex catalyzed hydration of nitrilesJournal of the American Chemical Society, 1993
- Ruthenium-catalyzed hydration of nitriles and transformation of .delta.-keto nitriles to ene-lactamsThe Journal of Organic Chemistry, 1992
- Kinetics and mechanism of nitrile hydration catalyzed by unhindered hydridobis(phosphine) platinum(II) complexes. Regioselective hydration of acrylonitrileJournal of the American Chemical Society, 1986