Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/27885
Title: Some ruthenium hydride, dihydrogen, and dihydrogen-bonded complexes in catalytic reactions
Authors: Lau, CP
Ng, SM
Jia, G
Lin, Z
Keywords: Catalysis
Dihydrogen bond
Dihydrogen complexes
Heterolytic cleavage
Hydride
Ruthenium
Issue Date: 2007
Publisher: Elsevier
Source: Coordination chemistry reviews, 2007, v. 251, no. 17-20, p. 2223-2237 How to cite?
Journal: Coordination chemistry reviews 
Abstract: The transfer of the hydrogen atoms from the η 2-H 2 ligand to the cis-disposed olefin ligand in a ruthenium olefin-dihydrogen complex is discussed. It is realized that H 2O and NEt 3 exhibit promoting effects in the catalytic hydrogenation of olefins with a couple of hydro(trispyrazolyl)borate (Tp)-supported ruthenium complexes. A reaction mechanism that accounts for the promoting effect has been proposed. A Tp-supported ruthenium solvento hydride complex TpRu(PPh 3)(CH 3CN)H was found to react with H 2 and R 3SiH to form the fluxional dihydrogen-hydride, and η 2-silane-hydride complexes, respectively. Although no stable and isolable σ-complex was formed with CH 4, the solvento hydride complex was found to be active in catalyzing H/D reactions of CH 4 with some deuterated common organic solvents. In the catalytic CO 2 hydrogenation reactions in THF/H 2O or alcohol, the complex TpRu(PPh 3)(CH 3CN)H generates the metal-ligand bifunctional catalyst TpRu(PPh 3)(ROH)H (R = H or alkyl) which transfers the hydride and a proton from ROH to the CO 2 molecule in a concerted manner, without coordination of the latter to the metal center. Aminocyclopentadienyl ruthenium complexes, which exhibit intramolecular Ru-H⋯H-N dihydrogen-bonding interactions were synthesized and characterized. These complexes provide good models for the study of heterolytic cleavage of η 2-H 2 ligand and its reverse-protonation of metal hydride to form dihydrogen complex. An indenyl ruthenium hydride complex was synthesized and found to be good catalyst for nitrile hydration reactions to give amides; these reactions nicely demonstrate the principle of utilizing dihydrogen bond to promote catalytic reactions.
URI: http://hdl.handle.net/10397/27885
ISSN: 0010-8545
EISSN: 1873-3840
DOI: 10.1016/j.ccr.2006.12.001
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