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Title: Mechanism of catalytic hydration of nitriles with hydrotris(pyrazolyl)borato (Tp) ruthenium complexes
Authors: Leung, CW
Zheng, W
Zhou, Z
Lin, Z
Lau, CP
Issue Date: 2008
Publisher: American Chemical Society
Source: Organometallics, 2008, v. 27, no. 19, p. 4957-4969 How to cite?
Journal: Organometallics 
Abstract: The aquo-amido complexes TpRu(PPh3)(H2O)(NHQO)R) (R = Me, Ph), which can be prepared by refluxing a THF solution of TpRu(PPh3)(RCN)H containing excess water or more conveniently by reacting TpRu(PPhARCN)CI with NaOH in THF in the presence of water, are found to be active for catalytic hydration of nitriles to amides. The catalysis proceeds via a mechanism that is distinctly different from the common ones involving intramolecular nucleophilic attack of a hydroxo (or aquo) ligand or external attack of a hydroxide ion (or water) at the carbon atom of the eta(1)-coordinated nitrile to form the metal amide intermediate and subsequent protonation of amido ligand by an adjacent aquo ligand or solvent water. The new mechanism involves the intermediacy of a relatively stable complex containing a chelating N-imidoylimidato ligand; ring-opening nucleophilic attack of this ligand by water is the product-generating step. Formation of the N-imidoylimidato complex from TpRu(PPhAH(2)O)(NHC(O)R) involves several steps. The initial one is displacement of the H2O ligand by a nitrile molecule to yield the nitrile-amido species TpRu(PPhARCN)(NHQO)R). This is followed by an unusual linkage isomerization of the N-bonded amido ligand to an O-bonded imido, which then undergoes nucleophilic attack at the carbon atom of the nitrile ligand in the complex; facile 1,3-proton shift between the nitrogen atoms on the resulting ring completes the reaction. The N-imidoylimidato complexes TpRu(PPh3)(kappa(2) -NO-NH= CMeN=CMeO), TpRu(PPh3)(kappa(2) -NO-NH=CPhN=CPhO), and TpRu(PPh3)(kappa(2)-N,O-NH=CMeN= CPhO) were independently prepared, and the molecular structure of TpRu(PPh3)kappa(2)-NO-NH=CPhN= CPhO) was determined by X-ray crystallography. To study the feasibility of the proposed mechanism for nitrile hydration with the aquo-amido complexes, theoretical calculations were performed at the Becke3LYP level of DFT theory to examine the whole catalytic cycle. It is learned that there is a substantially high barrier for the hydrolysis of the highly stable N-imidoylimidato complex, a step involving the ring-opening nucleophilic attack of this ligand by water, and this is probably the reason for the requirement of a relatively high reaction temperature.
ISSN: 0276-7333
EISSN: 1520-6041
DOI: 10.1021/om800474w
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